NL2024457B1 - Method for simultaneously recovering furfural product and sulfuric acid catalyst from furfural residue - Google Patents
Method for simultaneously recovering furfural product and sulfuric acid catalyst from furfural residue Download PDFInfo
- Publication number
- NL2024457B1 NL2024457B1 NL2024457A NL2024457A NL2024457B1 NL 2024457 B1 NL2024457 B1 NL 2024457B1 NL 2024457 A NL2024457 A NL 2024457A NL 2024457 A NL2024457 A NL 2024457A NL 2024457 B1 NL2024457 B1 NL 2024457B1
- Authority
- NL
- Netherlands
- Prior art keywords
- furfural
- sulfuric acid
- residue
- liquid
- evaporator
- Prior art date
Links
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 133
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 title claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 239000002351 wastewater Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- 230000008020 evaporation Effects 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims description 9
- 239000002028 Biomass Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000010802 sludge Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 230000000153 supplemental effect Effects 0.000 description 5
- 238000003915 air pollution Methods 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention discloses a method for simultaneously recovering a furfural product and a sulfuric acid catalyst from furfural residue. The method for simultaneously recovering the furfural product and the sulfuric acid catalyst from furfural residue includes 5 the following three steps: step 1, furfural residue is washed with circulating wastewater for dissolving residual furfural and sulfuric acid in the circulating wastewater; step 2, the mixture of the furfural residue and the circulating wastewater is subjected to solid—liquid separation; and step 3, the circulating wastewater in which the residual furfural and the sulfuric acid are dissolved is subjected to evaporation concentration in a wastewater 10 evaporator, and the product furfural and the catalyst sulfuric acid are simultaneously recovered. The method for simultaneously recovering the furfural product and the sulfuric acid catalyst from the furfural residue avoids additional energy consumption and water consumption, prevents the furfural and sulfuric acid in the furfural residue from polluting air, realizes yield increase of the furfural and recycling of the sulfuric acid catalyst, and 15 significantly improves the economic efficiency of furfural production.
Description
BACKGROUND Technical Field The present invention relates to a method for environmentally treating furfural residue, and in particular relates to a method for simultaneously recovering a furfural product and a sulfuric acid catalyst from furfural residue by using a wastewater evaporator in a furfural process. Related Art Furfural residue is the residual solid reaction product of furfural plants after furfural is extracted from corn cobs, mainly containing cellulose and lignin, and also containing a small part of residual unstripped furfural and a large part of sulfuric acid catalyst. At present, furfural plants use the furfural residue as boiler fuel. Before the furfural residue enters a boiler for combustion, the furfural residue containing water is baked by the residual heat of flue gas, so that the water content of the furfural residue is reduced to 35% or below, and then the furfural residue is fed into the boiler for combustion. However, in the process of baking the furfural residue, the atmospheric boiling point of an azeotrope formed by part of furfural and water remaining in the furfural residue is 79.7°C. The azeotrope of the furfural and water entering the atmosphere will cause air pollution. In addition, in the baking process, the sulfuric acid catalyst remaining in the furfural residue is also partially volatilized into the atmosphere, causing air pollution. After baking, part of the sulfuric acid still remaining in the furfural residue is combusted and decomposed into sulfur trioxide subsequently in a boiler furnace. If directly discharged into the atmosphere, the sulfur wuioxide will cause air pollution. If the sulfur trioxide is recovered by a desulfurization tower, higher equipment costs and operating costs are required. Therefore, there is an urgent need for a new technology suitable for environment-friendly treatment of furfural residue.
SUMMARY In order to overcome the defect of air pollution caused by residual furfural and sulfuric acid in the existing furfural treatment, the present invention provides a method for simultaneously recovering a furfural product and a sulfuric acid catalyst from furfural residue.
The technical solution adopted by the present invention to solve the technical problem thereof 1s as follows: step 1, furfural residue is washed with circulating wastewater for dissolving residual furfural and sulfuric acid in the circulating wastewater; step 2, the mixture of the furfural residue and the circulating wastewater is subjected to solid-liquid separation; and step 3, the circulating wastewater in which the residual furfural and the sulfuric acid are dissolved is subjected to evaporation concentration in a wastewater evaporator; mixed vapor of evaporated water, furfural and a small amount of sulfuric acid in the wastewater evaporator is introduced into the bottom of a reactor; the concentrated sulfuric acid solution at the bottom of the wastewater evaporator is mixed with a supplemental sulfuric acid solution as a circulating acid solution to enter a batching tank, and the mixed sulfuric acid solution is mixed with a biomass raw material in the batching tank; and the ingredients are fed into the reactor for reaction to produce furfural.
The specific operational flow of the technical solution of the present invention is as shown in the accompanying drawing, and the process is described as follows: furfural residue S1 and circulating wastewater S2 are mixed at a mass ratio of (1:2)-(1:4) and fully stirred in a washing tank 1; the furfural and the sulfuric acid remaining in the furfural residue are fully dissolved in the circulating wastewater S2; then a solid-liquid mixture S3 in the washing tank 1 is conveyed into a filter press 2 and subjected to solid-liquid separation; filter residue S4 is discharged into a filter residue tank 3 and used as boiler fuel when dried; filtrate S5 is input into an evaporator 4; the temperature of the evaporator 4 is controlled at 170-190°C; mixed vapor S7 of evaporated water vapor, furfural and a small amount of sulfuric acid 1s introduced into the bottom of a reactor 6; the water vapor is used as a stripping medium; the furfural and the newly produced furfural are stripped together out of the reactor and recovered; the sulfuric acid is trapped in a biomass raw material and liquid water to catalyze hydrolysis reaction of the biomass raw material; after the liquid at the bottom of the evaporator 4 is concentrated until the sulfuric acid mass content is 4%-6%, the liquid is input into an acid tank 7 as a concentrated sulfuric acid circulating liquid feed S8; after the concentrated sulfuric acid circulating liquid feed S8 is mixed with a supplemental sulfuric acid solution S11 having a sulfuric acid mass content of 5%, the mixed liquid is input into a batching tank 8 as a concentrated sulfuric acid circulating liquid discharge S9 and mixed with a solid biomass raw material at a liquid-to-solid ratio of (35:100)-(55:100); a mixture is input into the reactor 6 as a reactor feed S10; the reactor temperature is controlled at 170-190°C for reaction to produce furfural; a small amount of sludge S6 deposited at the bottom of the evaporator 4 is input into a sludge tank 5; and the sludge is dried to be used as a raw material for preparing carbon materials.
Compared with the prior art, the beneficial effects of the present invention are embodied as follows.
The method of the present invention uses the wastewater evaporator of furfural plants, achieves the effect of simultaneously recovering furfural and sulfuric acid from furfural residue, avoids additional energy consumption and water consumption, prevents the furfural and the sulfuric acid in the furfural residue from polluting air, realizes yield increase of the furfural and recycling of the sulfuric acid catalyst, and significantly improves the economic efficiency of furfural production.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of the process flow of the present invention.
Numbers in the drawing: 1 washing tank, 2 filter press, 3 filter residue tank, 4 evaporator, 5 sludge tank, 6 reactor, 7 acid tank, 8 batching tank, S1 furfural residue, S2 circulating wastewater, S3 solid-liquid mixture, S4 filter residue, S$ filtrate, S6 sludge, S7 mixed vapor, S8 concentrated sulfuric acid circulating liquid feed, S9 concentrated sulfuric acid circulating liquid discharge, S10 reactor feed, S11 supplemental sulfuric acid solution
DETAILED DESCRIPTION The present invention is further described below in conjunction with embodiments. Embodiment 1 Furfural residue S1 and circulating wastewater S2 were mixed at a mass ratio of 1:2.5 and fully stirred in a washing tank 1. The furfural and the sulfuric acid remaining in the furfural residue were fully dissolved in the circulating wastewater S2. Then a solid-liquid mixture S3 in the washing tank 1 was conveyed into a filter press 2 and subjected to solid-liquid separation. Filter residue S4 was discharged into a filter residue tank 3. Filtrate S5 was input into an evaporator 4. The temperature of the evaporator 4 was controlled at 180°C. Mixed vapor S7 of evaporated water, furfural and a small amount of sulfuric acid was introduced into the bottom of a reactor 6. After the liquid at the bottom of the evaporator 4 was concentrated until the sulfuric acid mass content was 5.4%, the liquid was input into an acid tank 7 as a concentrated sulfuric acid circulating liquid feed S8. After the concentrated sulfuric acid circulating liquid feed S8 was mixed with a supplemental sulfuric acid solution S11 having a sulfuric acid mass content of 5%, the mixed liquid was input into a batching tank 8 as a concentrated sulfuric acid circulating liquid discharge S9 and mixed with a solid biomass raw material at a liquid-to-solid ratio of 45:100. The mixture was input into the reactor 6 as a reactor feed S10. The reactor temperature was controlled at 180°C for reaction to produce furfural. A small amount of sludge S6 deposited at the bottom of the evaporator 4 was input into a sludge tank 5. The sludge was dried to be used as a raw material for preparing carbon materials. According to the above operation, the yield of furfural may be improved by 2%, and 95% of sulfuric acid may be recovered. Embodiment 2 Furfural residue S1 and circulating wastewater S2 were mixed at a mass ratio of 1:4 and fully stirred in a washing tank 1. The furfural and the sulfuric acid remaining in the furfural residue were fully dissolved in the circulating wastewater S2. Then a solid-liquid mixture S3 in the washing tank 1 was conveyed into a filter press 2 and subjected to solid-liquid separation.
Filter residue S4 was discharged into a filter residue tank 3. Filtrate S5 was input into an evaporator 4. The temperature of the evaporator 4 was controlled at 190°C.
Mixed vapor S7 of evaporated water, furfural and a small amount of sulfuric acid was introduced into the bottom of a reactor 6. After the liquid at the bottom of the 5 evaporator 4 was concentrated until the sulfuric acid mass content was 4.5%, the liquid was input into an acid tank 7 as a concentrated sulfuric acid circulating liquid feed S8. After the concentrated sulfuric acid circulating liquid feed S8 was mixed with a supplemental sulfuric acid solution S11 having a sulfuric acid mass content of 5%, the mixed liquid was input into a batching tank 8 as a concentrated sulfuric acid circulating liquid discharge S9 IO and mixed with a solid biomass raw material at a liquid-to-solid ratio of 55:100. The mixture was input into the reactor 6 as a reactor feed S10. The reactor temperature was controlled at 180°C for reaction to produce furfural.
A small amount of sludge S6 deposited at the bottom of the evaporator 4 was input into a sludge tank 5. The sludge was dried to be used as a raw material for preparing carbon materials.
According to the above operation, the yield of furfural may be improved by 1.5%, and 96% of sulfuric acid may be recovered.
It should be understood that the examples and embodiments described herein are merely illustrative and that various modifications and changes, made by those skilled in the art without departing from the spirit and scope of the present invention, fall within the scope of the present invention.
Claims (2)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910313410.4A CN110143937B (en) | 2019-04-18 | 2019-04-18 | Method for simultaneously recycling furfural product and sulfuric acid catalyst from furfural residues |
Publications (2)
Publication Number | Publication Date |
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NL2024457A NL2024457A (en) | 2020-10-22 |
NL2024457B1 true NL2024457B1 (en) | 2022-12-19 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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NL2024457A NL2024457B1 (en) | 2019-04-18 | 2019-12-13 | Method for simultaneously recovering furfural product and sulfuric acid catalyst from furfural residue |
Country Status (2)
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CN (1) | CN110143937B (en) |
NL (1) | NL2024457B1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN117482871B (en) * | 2024-01-03 | 2024-04-26 | 宁津禾洁生物科技有限公司 | Furfural extraction system for recycling low-emission furfural residues |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3842825A1 (en) * | 1988-01-08 | 1989-07-20 | Krupp Gmbh | METHOD AND DEVICE FOR PRODUCING FURFURAL |
CN1872726A (en) * | 2006-06-07 | 2006-12-06 | 济南圣泉集团股份有限公司 | Method for treating wastewater from furfural production |
CN100562519C (en) * | 2008-08-14 | 2009-11-25 | 宏业生化股份有限公司 | The method of producing furfural by cleaning hydrolysis of biomass |
CN102452645B (en) * | 2010-10-25 | 2013-07-17 | 山东金缘生物科技有限公司 | Process for recovering furfural and sulfuric acid from furfural residues |
CN103214045B (en) * | 2013-03-26 | 2015-09-16 | 河北科技大学 | A kind for the treatment of process of furfural waste-water |
-
2019
- 2019-04-18 CN CN201910313410.4A patent/CN110143937B/en active Active
- 2019-12-13 NL NL2024457A patent/NL2024457B1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
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CN110143937A (en) | 2019-08-20 |
CN110143937B (en) | 2023-05-16 |
NL2024457A (en) | 2020-10-22 |
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MM | Lapsed because of non-payment of the annual fee |
Effective date: 20240101 |