CN114956991B - Method for hydrothermally and co-producing organic acid by papermaking sludge - Google Patents
Method for hydrothermally and co-producing organic acid by papermaking sludge Download PDFInfo
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- CN114956991B CN114956991B CN202111316711.6A CN202111316711A CN114956991B CN 114956991 B CN114956991 B CN 114956991B CN 202111316711 A CN202111316711 A CN 202111316711A CN 114956991 B CN114956991 B CN 114956991B
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- 239000010802 sludge Substances 0.000 title claims abstract description 101
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000002893 slag Substances 0.000 claims abstract description 105
- 239000007787 solid Substances 0.000 claims abstract description 105
- 239000007788 liquid Substances 0.000 claims abstract description 89
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 39
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 30
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 30
- 239000001301 oxygen Substances 0.000 claims abstract description 30
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 28
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 23
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 17
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 17
- 238000004064 recycling Methods 0.000 claims abstract description 17
- 239000004310 lactic acid Substances 0.000 claims abstract description 15
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 15
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052663 cancrinite Inorganic materials 0.000 claims abstract description 14
- 235000019253 formic acid Nutrition 0.000 claims abstract description 14
- 235000011054 acetic acid Nutrition 0.000 claims abstract description 12
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 11
- 238000005272 metallurgy Methods 0.000 claims abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000002002 slurry Substances 0.000 claims description 37
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 18
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 230000007935 neutral effect Effects 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000001384 succinic acid Substances 0.000 claims description 9
- 239000002761 deinking Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- -1 small molecule organic acid Chemical class 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 33
- 229910052799 carbon Inorganic materials 0.000 abstract description 29
- 239000012071 phase Substances 0.000 abstract description 26
- 235000005985 organic acids Nutrition 0.000 abstract description 20
- 239000007791 liquid phase Substances 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 13
- 230000001105 regulatory effect Effects 0.000 abstract description 12
- 239000005416 organic matter Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000010335 hydrothermal treatment Methods 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 22
- 229910052791 calcium Inorganic materials 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 238000009423 ventilation Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 3
- 229920001046 Nanocellulose Polymers 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 229930091371 Fructose Natural products 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006833 benzilic acid rearrangement reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000006345 epimerization reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910006636 γ-AlOOH Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/50—Zeolites wherein inorganic bases or salts occlude channels in the lattice framework, e.g. sodalite, cancrinite, nosean, hauynite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/87—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by chromatography data, e.g. HPLC, gas chromatography
-
- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Treatment Of Sludge (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for carrying out hydro-thermal metallurgy and co-producing organic acid on papermaking sludge, which comprises the steps of carrying out hydro-thermal treatment on the papermaking sludge under the conditions of oxygen enrichment and alkalinity, and obtaining solid slag A and liquid A after centrifugal separation; regulating the pH value of the liquid A to 6.8-7.2, and then centrifugally separating to obtain solid slag B and liquid B; the liquid B is rich in small molecular organic acid; the main phase of the solid slag A is CaCO 3 And cancrinite, the main phase of the solid slag B is boehmite; the organic matter conversion rate of the papermaking sludge is 65.0-99.9%, the total organic carbon yield of the liquid phase is 65-99.9%, and the total organic carbon concentration of the liquid B is 5.0-13.5mg/mL, the liquid B contains oxalic acid, formic acid, acetic acid, lactic acid, glycollic acid, malonic acid and other organic acids, and the total carbon yield of the organic acids is 18.0-82.0%; the method has the advantages of simple process, easy operation, no need of drying pretreatment of the papermaking sludge, low reaction temperature and low energy consumption, and provides a new way for recycling the papermaking sludge.
Description
Technical Field
The invention relates to a method for hydrothermally and co-producing organic acid by papermaking sludge, belonging to the field of solid waste treatment and resource utilization.
Background
The papermaking sludge is solid waste generated in the papermaking wastewater treatment process and can be divided into primary sludge, secondary sludge and deinking sludge according to different sources. The papermaking sludge has high water content and complex components, and has the problem of difficult dehydration and difficult treatment. As shown in the literature, about 10765 ten thousand tons of paper and board were produced in the middle of 2019, whereas 1.2 tons of paper sludge (water content 80 wt%) was typically produced per 1 ton of paper produced, and thus about 1.29 hundred million tons of paper sludge were discharged per year in china. The large discharge of papermaking sludge not only brings serious threat to the ecological environment, but also brings heavy solid waste disposal pressure to papermaking enterprises. For a long time, most of the paper sludge has been treated by incineration and landfills. Harmful gases (such as NOx, SOx, aromatic hydrocarbons, dioxins) released from incineration cause serious damage to the atmosphere and human health. Sanitary landfills not only occupy a lot of land, but also cause secondary pollution to the surrounding environment, especially to soil and water. However, from the view point of the composition of the papermaking sludge, the papermaking sludge mainly contains organic matters such as cellulose, hemicellulose and the like and inorganic mineral fillers (calcium carbonate, talcum powder, kaolin and the like), which are potential recyclable resources, so that the development of reasonable and practical papermaking sludge recycling treatment technology is of great importance.
At present, the main recycling treatment technology of papermaking sludge comprises the steps of preparing biochar/activated carbon by high-temperature carbonization, preparing biological oil and biological synthesis gas by pyrolysis or gasification, preparing methane by anaerobic digestion, preparing ethanol by step/synchronous saccharification and fermentation, preparing nanocellulose by papermaking sludge and the like, wherein the biochar/activated carbon is used as a soil conditioner (or soil restoration agent), an adsorbent and a catalyst carrier. The high-temperature carbonization, pyrolysis and gasification processes not only need higher treatment temperature (carbonization: 500-800 ℃, pyrolysis: 400-900 ℃ and gasification: 700-1400 ℃), but also have strict requirements on the water content of papermaking sludge (according to literature data, the pyrolysis requires that the water content of sludge is lower than 20% and the water content of gasification sludge is not more than 35%), so that the method is not friendly to solid waste of papermaking sludge with high water content. Anaerobic digestion to produce marsh gas, stepwise/synchronous saccharification and fermentation to produce ethanol, while being capable of treating papermaking sludge with high water content, has long reaction process period and low product yield. There is also literature showing that nanocellulose can be successfully produced using cellulose contained in paper sludge, but nanocellulose yields are very low (0.8 wt.%), which severely limits the application of this process.
The content of the papermaking sludge water is higher than 97%, and the high-temperature and high-pressure water is directly utilized for treatment, so that not only can the dehydration and drying of the sludge be avoided, but also the rich water environment of the sludge can be fully utilized, and therefore, the hydrothermal method is one of effective ways for recycling the papermaking sludge. In the oxygen alkali environment, organic matters such as cellulose in the sludge can be converted into high-added-value platform compounds such as lactic acid and acetic acid by a hydrothermal method. In addition, more remarkable is that most of papermaking sludge recycling treatment technologies only focus on the conversion and application of organic components in sludge, but focus on the separation, enrichment and application of inorganic mineral components in sludge. Therefore, it is necessary to develop a method for simultaneously recycling organic matters and inorganic minerals in papermaking sludge, but no report is available at present.
Disclosure of Invention
Aiming at the problems and the defects existing in the prior art, the invention provides a method for hydrothermally and co-producing organic acid by papermaking sludge, which mainly comprises the steps of alkaline hydrolysis of cellulose and hemicellulose in papermaking sludge under an oxygen-enriched and alkaline environment to generate glucose, epimerization of the glucose to generate fructose, and further reaction of reverse aldol condensation, keto-enol tautomerism, dehydration, benzilic acid rearrangement, decarboxylation and the like of the glucose and the fructose to finally generate sodium salts of organic acid such as formic acid, acetic acid, lactic acid, malonic acid and the like. At the same time, al element is Al (OH) 4 - Dissolving the form in a strong alkaline solution, carrying out solid-liquid separation to obtain solid slag A (mainly comprising Ca components insoluble in alkaline conditions) and liquid A, regulating the pH value of the liquid A to be neutral, and separating out Al element dissolved in the strong alkaline solution in advance in a gamma-AlOOH form to obtain solid slag B; steaming organic acid in liquid phase productThe method has wide application after the subsequent treatments such as distillation or membrane separation; in addition, the main phases of the separated solid slag A are calcium carbonate, cancrinite and boehmite, and the solid slag A can be directly used as a catalyst for transesterification, hydrodeoxygenation, isomerization and other reactions after high-temperature calcination; the main phase of the solid slag B is boehmite, is an important precursor for preparing active alumina, and can be used in the fields of adsorption, catalysis and the like. In addition, the pH value of the liquid A can be regulated and controlled by changing the hydrothermal reaction temperature and time, so that the Al content in the solid slag A is regulated and controlled; the higher the pH value of the liquid A, the more obvious the separation of Ca and Al in the sludge, and the lower the Al content in the solid slag A; the lower the pH value of the liquid A, the more obvious the separation of organic matters and inorganic matters in the sludge, and the higher the Al content in the solid slag A; that is, the ratio of aluminum element in the solid slag A can be controlled by adjusting the reaction condition, so that the proportion of acid-base active sites in the catalyst can be regulated and controlled, and the effect of regulating and controlling the catalytic effect is achieved. Therefore, the invention can obtain the formic acid, lactic acid and other platform compounds and simultaneously realize the separation of organic-inorganic or Ca-Al components in the papermaking sludge, thereby realizing the recycling of the papermaking sludge to a greater extent.
The invention is realized by the following technical scheme:
a method for hydrothermally and co-producing organic acid by papermaking sludge comprises the following specific steps:
(1) Adding alkali liquor into papermaking sludge, and uniformly mixing to obtain slurry;
(2) Adding the slurry obtained in the step (1) into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, injecting oxygen, and carrying out hydrothermal reaction on papermaking sludge under the oxygen-enriched and alkaline conditions;
(3) After solid-liquid separation of the slurry after the reaction in the step (2), solid slag A and liquid A are obtained;
(4) Adjusting the pH value of the liquid A to 6.8-7.2, generating flocculent precipitate in the process, and carrying out solid-liquid separation on the suspension again to obtain solid slag B and liquid B; the liquid B is rich in organic acids such as oxalic acid, glycollic acid, formic acid, acetic acid, lactic acid, malonic acid, succinic acid and the like, and part of the liquid B exists in the form of acid radical ions;
(5) Washing solid slag A and solid slag B with deionized water to neutral, and dryingObtaining the material with the main contents of calcium and aluminum, wherein the main phase of the solid slag A is CaCO 3 And cancrinite, the main phase of the solid slag B is boehmite; and (3) after the washing water is collected, returning to the step (1) for recycling.
The papermaking sludge in the step (1) refers to papermaking primary sludge, papermaking secondary sludge or papermaking deinking sludge.
The alkali liquor in the step (1) is NaOH solution or KOH solution; the addition amount and concentration of alkali liquor are regulated according to the water content of papermaking sludge, so that the alkali concentration in the slurry is 0.5-2.0mol/L, and the water content of the slurry is 80% -98%.
The oxygen pressure in the high-pressure reaction kettle in the step (2) is 0.5-3.0MPa.
The temperature of the hydrothermal reaction in the high-pressure reaction kettle in the step (2) is 100-300 ℃, the reaction time is 1-20h, and the stirring speed of the reactor is 500-1000rpm.
The solid-liquid separation mode in the step (3) is centrifugation, vacuum filtration and standing sedimentation.
The mode used for adjusting the pH value in the step (4) is CO ventilation 2 Or HCl is added.
The invention converts organic matters such as cellulose, hemicellulose and the like in papermaking sludge into high added value chemicals such as organic acid and the like under the condition of oxygen alkali and water heating, and simultaneously utilizes the different dissolution characteristics of calcium and aluminum elements under the condition of strong alkalinity, and the pH value of a liquid phase A is regulated by regulating reaction conditions to separate Ca and Al components so as to obtain solid slag A (the main phase is CaCO) with the main content of calcium 3 And cancrinite) and a solid slag B (the main phase is boehmite) with the Al content as a main part; the invention carries out the oxygen-alkali water heating treatment on the papermaking sludge, and realizes the separation of organic-inorganic or Ca-Al components in the papermaking sludge while obtaining the platform compounds such as formic acid, lactic acid and the like so as to recover mineral components in the papermaking sludge, thereby realizing the high-value utilization of the mineral components.
The invention calculates the conversion rate of organic matters in papermaking sludge according to the formula (1):
the yield of liquid total organic carbon after hydrothermal reaction was calculated by formula (2):
the carbon yield of each organic acid in the liquid after the hydrothermal reaction was calculated by the formula (3):
calculating the distribution ratio of calcium or aluminum in the solid slag A, the solid slag B and the liquid B according to the formula (4):
compared with the prior art, the invention has the following advantages and effects:
(1) When the invention is used for treating papermaking sludge, not only can organic components in the sludge be converted into organic acid and other platform compounds, but also the effective separation of organic-inorganic components or Ca-Al components in the sludge can be realized, the main phases of the solid slag A obtained after treatment are calcium carbonate, cancrinite and boehmite, the solid slag A can be used as a catalyst for transesterification, hydrodeoxygenation, isomerization and other reactions after high-temperature calcination, the proportion of aluminum element in the solid slag A can be controlled by adjusting the reaction conditions, and the proportion of acid-alkali active sites in the catalyst can be regulated and controlled, thereby playing the role of regulating and controlling the catalytic effect; the main phase of the solid slag B is boehmite, is an important precursor for preparing activated alumina, can be used in the fields of adsorption, catalysis and the like, and can realize the recycling of organic components and inorganic components in papermaking sludge simultaneously through the technical scheme of the invention.
(2) The organic matter conversion rate of the papermaking sludge is 65.0-99.9%; the yield of the liquid phase total organic carbon is 65.0-99.9%, and the concentration of the total organic carbon is 5.0-13.5mg/mL; the liquid phase B contains oxalic acid, formic acid, acetic acid, lactic acid, glycollic acid, malonic acid and other organic acids, and the total carbon yield of the organic acids is 18.0-82.0%.
(3) The technology for treating the papermaking sludge has the advantages of simple process, easy operation, no need of drying pretreatment of the papermaking sludge, low reaction temperature and low energy consumption; the research result provides a new way for the resource utilization of papermaking sludge.
Drawings
FIG. 1 is an XRD pattern of solid slag A;
FIG. 2 is an XRD pattern of solid slag B;
FIG. 3 is an EDS energy spectrum of solid slag B;
FIG. 4 is a chromatogram of liquid B;
FIG. 5 shows the detection of other organic acids in liquid B by GCMS.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
Example 1
A method for hydrothermally and co-producing organic acid by papermaking sludge comprises the following specific steps:
(1) Uniformly mixing 1g of papermaking secondary sludge (the water content is 1.3 wt%, all the contents are mass percent content) with 20mL of 0.5mol/L KOH solution, and standing for 48h, wherein the alkali concentration in the prepared slurry is 0.5mol/L, and the water content of the slurry is 95.3%;
(2) Uniformly mixing the slurry obtained in the step (1), adding the mixture into a high-pressure reaction kettle, sealing the reaction kettle, purging the reaction kettle with oxygen for three times, and injecting 0.5MPa high-purity oxygen;
(3) Carrying out hydrothermal reaction on the papermaking sludge under the oxygen-enriched and alkaline conditions, wherein the hydrothermal reaction temperature is 100 ℃, the reaction time is 1h, the stirring speed is 800rpm, and cooling to room temperature after the reaction is finished;
(4) Centrifugally separating the slurry obtained after the reaction in the step (3) to obtain solid slag A and liquid A, wherein the pH value of the liquid A is 13.13;
(5) CO ventilation 2 Adjusting the pH value of the liquid A to 7.0, generating flocculent precipitate in the process, and carrying out solid-liquid centrifugal separation on the suspension again to obtain solid slag B and liquid B;
(6) Washing the solid slag A and the solid slag B with deionized water to be neutral, and drying to obtain materials mainly containing calcium and aluminum respectively; the main phase of the solid slag A is CaCO 3 And cancrinite, the main phase of the solid slag B is boehmite; and (3) after the washing water is collected, returning to the step (1) for recycling.
The organic matter conversion rate of the papermaking sludge is 65.1 percent; the yield of the liquid phase total organic carbon is 67.2%, and the concentration of the total organic carbon is 5.08mg/mL; the liquid B contains oxalic acid, formic acid, acetic acid, lactic acid, glycollic acid, malonic acid, succinic acid and other organic acids, the total carbon yield of the organic acids is 18.4%, and the distribution ratio of Ca element in the solid slag A, the solid slag B and the liquid B is 91.8%,1.9% and 6.2%; the distribution ratio of the Al element in the solid slag a, the solid slag B, and the liquid B was 6.4%,91.1%,2.1%.
Example 2
A method for hydrothermally and co-producing organic acid by papermaking sludge comprises the following specific steps:
(1) Uniformly mixing 1g of papermaking secondary sludge (with the water content of 1.3 wt.%) with 20mL of KOH solution with the water content of 0.5mol/L, standing for 24h, wherein the alkali concentration in the prepared slurry is 0.5mol/L, and the water content of the slurry is 95.3%;
(2) Uniformly mixing the slurry obtained in the step (1), adding the mixture into a high-pressure reaction kettle, sealing the reaction kettle, purging the reaction kettle with oxygen for three times, and injecting high-purity oxygen of 1.5 MPa;
(3) Carrying out hydrothermal reaction on the papermaking sludge under the oxygen-enriched and alkaline conditions, wherein the hydrothermal reaction temperature is 140 ℃, the reaction time is 2 hours, the stirring speed is 800rpm, and cooling to room temperature after the reaction is finished;
(4) Centrifugally separating the slurry obtained after the reaction in the step (3) to obtain solid slag A and liquid A, wherein the pH value of the liquid A is 12.86;
(5) CO ventilation 2 Adjusting the pH value of the liquid A to 7.2, generating flocculent precipitate in the process, and carrying out solid-liquid separation on the suspension again to obtain solid slag B and liquid B;
(6) Washing the solid slag A and the solid slag B with deionized water to be neutral, and drying to obtain materials mainly containing calcium and aluminum respectively; the main phase of the solid slag A is CaCO 3 And cancrinite, the main phase of the solid slag B is boehmite; and (3) after the washing water is collected, returning to the step (1) for recycling.
The organic matter conversion rate of the papermaking sludge in the embodiment is 70.2%; the yield of the liquid phase total organic carbon is 70.6%, and the concentration of the total organic carbon is 6.07mg/mL; the liquid B contains oxalic acid, formic acid, acetic acid, lactic acid, glycollic acid, malonic acid, succinic acid and other organic acids, and the total carbon yield of the organic acids is 21.6%; the distribution ratio of Ca element in the solid slag A, the solid slag B and the liquid B is 90.3%,2.4% and 7.1%; the distribution ratio of the Al element in the solid slag a, the solid slag B, and the liquid B was 8.2%,82.4%,9.2%.
Example 3
A method for hydrothermally and co-producing organic acid by papermaking sludge comprises the following specific steps:
(1) Uniformly mixing 2g of papermaking secondary sludge (with the water content of 1.3 wt.%) with 20mL of KOH solution with the water content of 1.2mol/L, standing for 24h, wherein the alkali concentration in the prepared slurry is 1.2mol/L, and the water content of the slurry is 91.03%;
(2) Uniformly mixing the slurry obtained in the step (1), adding the mixture into a high-pressure reaction kettle, sealing the reaction kettle, purging the reaction kettle with oxygen for three times, and injecting high-purity oxygen of 1.3 MPa;
(3) Carrying out hydrothermal reaction on the papermaking sludge under the oxygen-enriched and alkaline conditions, wherein the hydrothermal reaction temperature is 150 ℃, the reaction time is 2 hours, the stirring speed is 800rpm, and cooling to room temperature after the reaction is finished;
(4) Centrifugally separating the slurry obtained after the reaction in the step (3) to obtain solid slag A and liquid A, wherein the pH value of the liquid A is 12.71;
(5) CO ventilation 2 Adjusting the pH value of the liquid A to 6.9, generating flocculent precipitate in the process, and carrying out solid-liquid separation on the suspension again to obtain solid slag B and liquid B;
(6) Washing the solid slag A and the solid slag B with deionized water to be neutral, and drying to obtain materials mainly containing calcium and aluminum respectively; the main phase of the solid slag A is CaCO 3 And cancrinite, the main phase of the solid slag B is boehmite; and (3) after the washing water is collected, returning to the step (1) for recycling.
The organic matter conversion rate of the papermaking sludge in the embodiment is 77.7%; the yield of the liquid phase total organic carbon is 72.9%, and the concentration of the total organic carbon is 7.12mg/mL; the liquid B contains oxalic acid, formic acid, acetic acid, lactic acid, glycollic acid, malonic acid, succinic acid and other organic acids, and the total carbon yield of the organic acids is 39.8%; the distribution ratio of Ca element in the solid slag A, the solid slag B and the liquid B is 92.3 percent, 1.9 percent and 5.5 percent; the distribution ratio of the Al element in the solid slag A, the solid slag B and the liquid B was 10.6%,78.4% and 8.9%.
Example 4
A method for hydrothermally and co-producing organic acid by papermaking sludge comprises the following specific steps:
(1) Uniformly mixing 2g of papermaking primary sludge (with the water content of 50.6 wt.%) with 20mL of 1.1mol/L NaOH solution, standing for 24h, wherein the alkali concentration in the prepared slurry is 1.05mol/L, and the water content of the slurry is 95.5%;
(2) Uniformly mixing the slurry obtained in the step (1), adding the mixture into a high-pressure reaction kettle, sealing the reaction kettle, purging the reaction kettle with oxygen for three times, and injecting high-purity oxygen of 1.4 MPa;
(3) Carrying out hydrothermal reaction on the papermaking sludge under the oxygen-enriched and alkaline conditions, wherein the hydrothermal reaction temperature is 160 ℃, the reaction time is 2 hours, the stirring speed is 800rpm, and cooling to room temperature after the reaction is finished;
(4) Centrifugally separating the slurry obtained after the reaction in the step (3) to obtain solid slag A and liquid A, wherein the pH value of the liquid A is 12.59;
(5) CO ventilation 2 Adjusting the pH value of the liquid A to 6.8, generating flocculent precipitate in the process, and carrying out solid-liquid separation on the suspension again to obtain solid slag B and liquid B;
(6) Washing the solid slag A and the solid slag B with deionized water to be neutral, and drying to obtain materials mainly containing calcium and aluminum respectively; the main phase of the solid slag A is CaCO 3 And cancrinite, the main phase of the solid slag B is boehmite; and (3) after the washing water is collected, returning to the step (1) for recycling.
The organic matter conversion rate of the papermaking sludge is 80.5%; the yield of the liquid phase total organic carbon is 74.1 percent, and the concentration of the total organic carbon is 8.22mg/mL; the liquid B contains oxalic acid, formic acid, acetic acid, lactic acid, glycollic acid, malonic acid, succinic acid and other organic acids, and the total carbon yield of the organic acids is 44.9%; the distribution ratio of Ca element in the solid slag A, the solid slag B and the liquid B is 93.8 percent, 1.4 percent and 2.7 percent; the distribution ratio of the Al element in the solid slag A, the solid slag B and the liquid B was 16.3%,75.1% and 8.4%.
Example 5
A method for hydrothermally and co-producing organic acid by papermaking sludge comprises the following specific steps:
(1) Uniformly mixing 2g of papermaking deinking sludge (the water content is 50.6 wt.%) with 20mL of KOH solution with the concentration of 2mol/L, standing for 24h, wherein the alkali concentration in the prepared slurry is 1.9mol/L, and the water content of the slurry is 95.5%;
(2) Uniformly mixing the slurry obtained in the step (1), adding the mixture into a high-pressure reaction kettle, sealing the reaction kettle, purging the reaction kettle with oxygen for three times, and injecting high-purity oxygen of 2.5 MPa;
(3) Carrying out hydrothermal reaction on the papermaking sludge under the oxygen-enriched and alkaline conditions, wherein the hydrothermal reaction temperature is 180 ℃, the reaction time is 4 hours, the stirring speed is 800rpm, and cooling to room temperature after the reaction is finished;
(4) Filtering and separating the slurry obtained after the reaction in the step (3) to obtain solid slag A and liquid A, wherein the pH value of the liquid A is 11.17;
(5) CO ventilation 2 Adjusting the pH value of the liquid A to 7.1, generating flocculent precipitate in the process, and carrying out solid-liquid separation on the suspension again to obtain solid slag B and liquid B;
(6) Washing the solid slag A and the solid slag B with deionized water to be neutral, and drying to obtain materials mainly containing calcium and aluminum respectively; the main phase of the solid slag A is CaCO 3 And cancrinite, the main phase of the solid slag B is boehmite; and (3) after the washing water is collected, returning to the step (1) for recycling.
The conversion rate of the papermaking sludge in the embodiment is 89.5%; the yield of the liquid phase total organic carbon is 82.7%, and the concentration of the total organic carbon is 8.79mg/mL; the liquid B contains oxalic acid, formic acid, acetic acid, lactic acid, glycollic acid, malonic acid, succinic acid and other organic acids, and the total carbon yield of the organic acids is 65.8%; the distribution ratio of Ca element in the solid slag A, the solid slag B and the liquid B is 94.3 percent, 1.2 percent and 3.8 percent; the distribution ratio of the Al element in the solid slag a, the solid slag B, and the liquid B was 38.7%,51.2%,8.6%.
FIG. 1 is an XRD pattern of solid slag A obtained in examples 1-5, from which it is seen that the main phases in solid slag A are calcium carbonate, cancrinite, boehmite; FIGS. 2 and 3 show XRD patterns and EDS spectra of solid slag B obtained in examples 1 to 4, respectively, in which boehmite is a main phase.
Example 6
A method for hydrothermally and co-producing organic acid by papermaking sludge comprises the following specific steps:
(1) Uniformly mixing 1g of papermaking secondary sludge (with the water content of 1.3 wt.%) with 20mL of 1mol/L NaOH solution, and standing for 24h, wherein the alkali concentration in the prepared slurry is 1mol/L, and the water content of the slurry is 95.3%;
(2) Uniformly mixing the slurry obtained in the step (1), adding the mixture into a high-pressure reaction kettle, sealing the reaction kettle, purging the reaction kettle with oxygen for three times, and injecting high-purity oxygen of 3.0 MPa;
(3) Carrying out hydrothermal reaction on the papermaking sludge under the oxygen-enriched and alkaline conditions, wherein the hydrothermal reaction temperature is 200 ℃, the reaction time is 2 hours, the stirring speed is 1000rpm, and cooling to room temperature after the reaction is finished;
(4) Standing, settling and separating the slurry obtained after the reaction in the step (3) to obtain solid slag A and liquid A, wherein the pH value of the liquid A is 9.84;
(5) CO ventilation 2 Adjusting the pH value of the liquid A to 6.9, generating flocculent precipitate in the process, and carrying out solid-liquid separation on the suspension again to obtain solid slag B and liquid B;
(6) Washing the solid slag A and the solid slag B with deionized water to be neutral, and drying to obtain materials mainly containing calcium and aluminum respectively; the main phase of the solid slag A is CaCO 3 And cancrinite, the main phase of the solid slag B is boehmite; and (3) after the washing water is collected, returning to the step (1) for recycling.
The conversion rate of the papermaking sludge in the embodiment is 95.5%; the yield of the liquid phase total organic carbon is 93.7%, and the concentration of the total organic carbon is 10.26mg/mL; the liquid B contains organic acids such as oxalic acid, formic acid, acetic acid, lactic acid, glycollic acid, malonic acid, succinic acid and the like, the total carbon yield of the organic acids is 72.48 percent, the liquid B is subjected to liquid phase analysis and detection after the pH value of the liquid B is regulated to be 3, wherein the HPLC (high performance liquid chromatography) chromatogram of each target organic acid is shown in figure 4, and other components in the liquid phase are detected by GC-MS, and the result is shown in figure 5; the distribution ratio of Ca element in the solid slag A and the liquid A is 95.3 percent, 3.8 percent; the distribution ratio of the Al element in the solid slag a and the liquid a was 92.7%,4.9%.
Example 7
A method for hydrothermally and co-producing organic acid by papermaking sludge comprises the following specific steps:
(1) Uniformly mixing 1g of papermaking secondary sludge (with the water content of 1.3 wt.%) with 20mL of 1mol/L NaOH solution, and standing for 36h, wherein the alkali concentration in the prepared slurry is 1mol/L, and the water content of the slurry is 95.3%;
(2) Uniformly mixing the slurry obtained in the step (1), adding the mixture into a high-pressure reaction kettle, sealing the reaction kettle, purging the reaction kettle with oxygen for three times, and injecting high-purity oxygen of 2.0 MPa;
(3) Carrying out hydrothermal reaction on the papermaking sludge under the oxygen-enriched and alkaline conditions, wherein the hydrothermal reaction temperature is 300 ℃, the reaction time is 20 hours, the stirring speed is 500rpm, and cooling to room temperature after the reaction is finished;
(4) Centrifugally separating the slurry obtained after the reaction in the step (3) to obtain solid slag A and liquid A, wherein the pH value of the liquid A is 9.08;
(5) CO ventilation 2 Adjusting the pH value of the liquid A to 6.9, generating flocculent precipitate in the process, and carrying out solid-liquid separation on the suspension again to obtain solid slag B and liquid B;
(6) Washing the solid slag A and the solid slag B with deionized water to be neutral, and drying to obtain materials mainly containing calcium and aluminum respectively; the main phase of the solid slag A is CaCO 3 And cancrinite, the main phase of the solid slag B is boehmite; and (3) after the washing water is collected, returning to the step (1) for recycling.
The conversion rate of the papermaking sludge in the embodiment is 99.9%; the yield of the liquid phase total organic carbon is 96.4%, and the concentration of the total organic carbon is 13.49mg/mL; the liquid B contains oxalic acid, formic acid, acetic acid, lactic acid, glycollic acid, malonic acid, succinic acid and other organic acids, and the total carbon yield of the organic acids is 82.2%; the distribution ratio of Ca element in the solid slag A and the liquid A is 96.2 percent, 2.9 percent; the distribution ratio of the Al element in the solid slag a and the liquid a was 94.2%,5.1%.
In the above specific examples, the inorganic components Ca and Al in examples 1 to 4 have a remarkable separation effect; the organic and inorganic mineral components of the sludge of examples 6-7 have a significant separation effect.
The embodiments and objects of the present invention are not limited by the examples described above, and any other changes, modifications, substitutions, combinations, and simplifications that are made without departing from the spirit and principles of the invention are intended to be equivalent substitutes and are also within the scope of the invention.
Claims (7)
1. A method for hydrothermally and co-producing organic acid by papermaking sludge is characterized by comprising the following specific steps:
(1) Adding alkali liquor into papermaking sludge, and uniformly mixing to obtain slurry;
(2) Adding the slurry obtained in the step (1) into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, and then injecting oxygen for hydrothermal reaction;
(3) Carrying out solid-liquid separation on the slurry obtained after the reaction in the step (2) to obtain solid slag A and liquid A;
(4) Adjusting the pH value of the liquid A to 6.8-7.2, and then carrying out solid-liquid separation to obtain solid slag B and liquid B; the liquid B is rich in small molecule organic acid;
(5) Washing solid slag A and solid slag B with deionized water to neutral, and drying to obtain CaCO as the main phase of solid slag A 3 And cancrinite, the main phase of the solid slag B is boehmite.
2. The method for the hydrothermal metallurgy and co-production of organic acid according to claim 1, wherein the papermaking sludge in the step (1) is one of primary sludge in papermaking, secondary sludge in papermaking and deinking sludge in papermaking.
3. The method for hydrothermally producing paper sludge and co-producing organic acid according to claim 1, wherein the alkali liquor in the step (1) is NaOH solution or KOH solution; the alkali concentration in the slurry is 0.5-2.0mol/L, and the water content is 80% -98%.
4. The method for the hydrothermal metallurgy and co-production of organic acid according to claim 1, wherein the oxygen pressure in the high-pressure reaction vessel in the step (2) is 0.5 to 3.0MPa.
5. The method for hydrothermally producing organic acid and co-producing the same according to claim 1, wherein the temperature of the hydrothermal reaction in the high-pressure reaction kettle in the step (2) is 100-300 ℃, the reaction time is 1-20h, and the stirring speed of the reactor is 500-1000rpm.
6. The method for hydrothermally producing paper sludge and co-producing organic acid according to claim 1, wherein the small molecular organic acid in the step (4) is oxalic acid, glycollic acid, formic acid, acetic acid, lactic acid, malonic acid or succinic acid.
7. The method for hydrothermally and co-producing organic acid according to claim 1, wherein the washing water in the step (5) is collected and returned to the step (1) for recycling.
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