CN109569442A - A method of O3 catalytic oxidation method is used for wood vinegar and decolourizes and prepares calcium acetate magnesium salt - Google Patents
A method of O3 catalytic oxidation method is used for wood vinegar and decolourizes and prepares calcium acetate magnesium salt Download PDFInfo
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- CN109569442A CN109569442A CN201811321956.6A CN201811321956A CN109569442A CN 109569442 A CN109569442 A CN 109569442A CN 201811321956 A CN201811321956 A CN 201811321956A CN 109569442 A CN109569442 A CN 109569442A
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- wood vinegar
- conversion fluid
- calcium
- magnesium
- ozone
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- 239000000052 vinegar Substances 0.000 title claims abstract description 87
- 235000021419 vinegar Nutrition 0.000 title claims abstract description 87
- 239000002023 wood Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 15
- 230000003647 oxidation Effects 0.000 title claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 13
- ZORPJCONVDWMSP-UHFFFAOYSA-J calcium;magnesium;tetraacetate Chemical compound [Mg+2].[Ca+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O ZORPJCONVDWMSP-UHFFFAOYSA-J 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 239000012530 fluid Substances 0.000 claims abstract description 53
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 30
- 239000013049 sediment Substances 0.000 claims abstract description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000011575 calcium Substances 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000011777 magnesium Substances 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 26
- 239000000395 magnesium oxide Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 230000005587 bubbling Effects 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 238000004042 decolorization Methods 0.000 claims description 3
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000004061 bleaching Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 10
- 238000006385 ozonation reaction Methods 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 8
- 239000011654 magnesium acetate Substances 0.000 description 7
- 235000011285 magnesium acetate Nutrition 0.000 description 7
- 229940069446 magnesium acetate Drugs 0.000 description 7
- 239000005416 organic matter Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- -1 Hydroxyl radical free radical Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 4
- 239000001639 calcium acetate Substances 0.000 description 4
- 235000011092 calcium acetate Nutrition 0.000 description 4
- 229960005147 calcium acetate Drugs 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000005413 snowmelt Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 229920000862 Arboform Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001662103 Cryptocarya corrugata Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HFNUUHLSQPLBQI-UHFFFAOYSA-N acetic acid;calcium Chemical compound [Ca].CC(O)=O HFNUUHLSQPLBQI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- YLUIKWVQCKSMCF-UHFFFAOYSA-N calcium;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Ca+2] YLUIKWVQCKSMCF-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
-
- 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
- C01F11/02—Oxides or hydroxides
- C01F11/04—Oxides or hydroxides by thermal decomposition
-
- 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
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
- C01F5/06—Magnesia by thermal decomposition of magnesium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method of O3 catalytic oxidation method is used for wood vinegar and decolourizes and prepares calcium acetate magnesium salt, it is mainly: 1) solid alkaline object being added into wood vinegar, it includes calcium or the oxides and hydroxide of magnesium, react 1-2 hours at room temperature, make its pH value in 7-8；2) dark brown wood vinegar conversion fluid is filtered to take；3) solid alkaline object described in step 1 is added into wood vinegar conversion fluid, additional amount 2-10g/L makes pH=8-11；4) ozone, O are passed through to the wood vinegar conversion fluid that step 3 obtains3Concentration is 90-120mg/L, flow velocity 200-1000mL/min, reacts 3-5h；5) wood vinegar conversion fluid pH value is adjusted after the completion of decoloration close to neutrality, filters, low-carbon calcium magnesium carboxylate aqueous solution is taken to be sprayed；6) solid sediment that step 5 filters out is roasted at 800 DEG C.Simple production process of the present invention, low in cost, bleaching time is short, energy-efficient, without secondary pollution, and comprehensive utilization ratio is high.
Description
Technical field
The present invention relates to wood vinegar discoloration methods.
Background technique
Ice is replaced using the waste liquid (wood vinegar) generated in biomass waste material (wheat straw bar, sawdust etc.) gasification, retort process
Acetic acid is reacted with dolomite dust, by processes such as conversion, decoloration, evaporative crystallizations, develops calcium acetate magnesium salt (CMA) class of white
Plant base composite snow-melting agent.By biomass waste liquid CMA class environment-friendly snowmelt agent, it can not only be avenged for road deicing and a kind of warp is provided
Help feasible environment-friendly snowmelt agent, eradicates deicing salt chlorine evil, while can provide one for the improvement of this biolobic material waste liquid and become useless
For precious new way.But this link of decolourizing during wood vinegar production deicing salt, generallys use active carbon decoloring method
(CN203474707U), the shortcoming of this mode is higher cost.
Summary of the invention
The object of the present invention is to provide a kind of simple process and low costs, and comprehensive utilization ratio is high, environmentally protective, without secondary
O3 catalytic oxidation method is used for the method that wood vinegar decolourizes and prepares calcium acetate magnesium salt by pollution.The present invention is mainly used and is urged
Change the mode combined with ozone, accelerate the degradation rate of the aromatic series organic matter such as phenol in wood vinegar, shorten the decoloring reaction time,
Ozone utilization efficiency is improved, to realize the purpose of quick decolorization.
The specific steps of the present invention are as follows:
1, solid alkaline object is added into wood vinegar, it includes calcium or the hydroxide of magnesium oxide or calcium or magnesium, rooms
It is stirred evenly under temperature, reacts 1-2 hours, make its pH value in 7-8.The effect of the solid alkaline object in this step is to neutralize wood
Vinegar liquid, to obtain the wood vinegar conversion fluid of weakly acidic pH.
2, filtering removal insoluble matter, obtains dark brown wood vinegar conversion fluid.
3, solid alkaline object described in step 1, additional amount 2-10g/L are added into wood vinegar conversion fluid, and are carried out
Stirring, makes pH=8-11, the effect of the solid alkaline object in this step is catalyst.
4, it is passed through ozone to the wood vinegar conversion fluid that step 3 obtains, is the mixed gas generated by ozone generator, it should
Mixed gas is the gaseous mixture of ozone and oxygen, wherein O3Concentration is 90-120mg/L, flow velocity 200-1000mL/min, reaction
3-5h, the wood vinegar conversion fluid that best mixed gas is obtained by the SPG membrane continuous bubbling of reactor bottom to step 3
In, with the extension for being passed through ozonation time, wood vinegar conversion fluid color is gradually changed by dark brown faint yellow or close to colourless.
Since wood vinegar conversion fluid and ozone reaction are continuous acidizations, pH value can be reduced.Preferably, in oxidative degradation decolorization
In, solid alkaline object described in step 1 is continuously replenished, wood vinegar conversion fluid pH is made to be maintained at 8 ± 0.5, it is smelly that catalysis can be shortened in this way
The oxygen oxidative decoloration time.
5, if wood vinegar conversion fluid pH value is lower than 7 after the completion of decolourizing, the solid alkaline object can be added, adjust wood vinegar
Conversion fluid pH value obtains low-carbon calcium magnesium carboxylate (mainly calcium acetate magnesium salt) aqueous solution, further by filtering close to neutrality
It obtains approaching the white low-carbon calcium magnesium carboxylate solid powder based on calcium acetate magnesium salt by being spray-dried, snow melt can be done
Agent.
It is dry 6. the solid sediment that step 5 is filtered out washs, roasted at 800 DEG C calcium oxide (magnesium) can be made
Recycling is repeated for catalyst.
The working principle of the invention approximately as: due to aromatic series organic matters such as the phenol that contains in wood vinegar, and phenols
Substance can be oxidized in air, can gradually be become dark-brown (quinoid structure of conjugated system), be caused wood vinegar color deeper.
Ozonation can make polycyclic aromatic hydrocarbon, heterocyclic compound and long-chain molecule portion fractures, and macromolecular complex is made to be changed into small molecule object
Matter.The oxidation activity of acetic acid is relatively low, and ozone Oxidation Treatment technique does not need the input of high-energy, to solution coloration etc.
Characteristic dependence is lower, and reaction condition is mild.It is stronger that ozone can form reaction rate height, oxidisability under the effect of the catalyst
Hydroxyl radical free radical, oxidation rate are much larger than the rate directly ozonized.
The invention has the following advantages over the prior art:
1. simple production process, low in cost, O3 catalytic oxidation can produce reactivity more compared with independent ozonisation
Strong hydroxyl radical free radical shortens bleaching time, energy-efficient.
2. solid alkaline object is both raw material and catalyst, and cheap, environmental protection be can dissolve in product, be generated
Calcium acetate or magnesium acetate, without secondary pollution, comprehensive utilization ratio is high.
3. the insoluble sediment calcium oxalate or magnesium oxalate that filter out after the completion of decoloration are recyclable, dry by washing, roasting
It burns and generates calcium oxide or magnesia again, recycling recycling.
Detailed description of the invention
Fig. 1 is the wood vinegar conversion fluid degradation effect material object photo figure that embodiment 1 leads to ozone different time.
Fig. 2 is each time ultraviolet-visible of embodiment 1 scanning full figure.
Fig. 3 is the XRD diagram of 1 residual solid insoluble matter of embodiment.
Fig. 4 is the TIC figure of 6 raw material wood vinegar organic phase of embodiment.
Fig. 5 is the TIC figure of 6 no bleaching wood vinegar conversion fluid organic phase of embodiment.
Fig. 6 is the TIC figure of organic phase after 6 O3 catalytic oxidation wood vinegar conversion fluid 4h of embodiment.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Embodiment 1
Calcium oxide is added into wood vinegar, stirs evenly at room temperature, reacts 1.5 hours, makes its pH value 7.5.It filters off
Except insoluble matter, dark brown wood vinegar conversion fluid is obtained.1g calcium oxide, which is added, into 250mL wood vinegar conversion fluid (is equivalent to 4g/
L), and it is stirred, measuring its pH value is 9.5.The wood vinegar conversion fluid upward obtained is passed through ozone, is occurred by ozone
The ozone and oxygen mixed gas that device generates, wherein O3Concentration is 90mg/L, flow velocity 200mL/min, which passes through
The SPG membrane continuous bubbling of reactor bottom is into wood vinegar conversion fluid.With the extension for being passed through ozonation time, wood vinegar turns
Change liquid color be gradually changed by dark brown it is faint yellow or close to colourless.Fig. 1 is embodiment 1 in catalytic ozonation decolored degradation
The degradation effect material object photo figure to wood vinegar conversion fluid is promoted in reaction at any time.Wherein, 1#It is not treated by ozone, 2-6#Point
Ozone treatment 10min, 30min, 60min, 120min and 180min Wei not passed through, it can be seen that after 60min, wood vinegar conversion
Liquid is obviously thin out, almost colourless after 180min.Supernatant liquor is taken respectively, dilutes 25 times, with easy spectrophotometry
Meter is detected, and result is as shown in Figure 2.Fig. 2 is each time ultraviolet-visible scanning full figure of embodiment 1, is usually saturated organic
For object near ultraviolet band without absorption, the organic matter containing conjugated double bond or phenyl ring has apparent absorption or characteristic peak in ultra-violet (UV) band, contains benzene
The main absorbing wavelength of the simple aromatic compound of ring is in 250-260nm [Jiang Shaojie, Liu Zongyuan .UV254As in water process
Meaning [J] Chongqing Univ. of Architecture journal of organic matter Con trolling index, 2002,24 (2): 61-65].Due in alkaline medium,
Phenol can form phenol anion, and maximum absorption wavelength moves to 290nm from 270nm.Before the reaction in 10min, because of phenol
Substance is oxidized to quinones first, and color burn increased in visible-range internal absorbance value.But not with ozone
It is open close enter, be all decreased obviously in entire sweep interval absorbance value.
After the completion of decoloration, test wood vinegar conversion fluid pH value is 6, and calcium oxide is added and adjusts during wood vinegar conversion fluid pH value is
Property, calcium acetate aqueous solution is obtained by filtering, further obtains approaching the calcium acetate solid powder of white by spray drying.It takes out
Obtained solid sediment is filtered, is washed, it is dry, by XRD analysis, compares, confirm insoluble solid with the standard card of calcium oxalate
Body object is calcium oxalate, as shown in figure 3, roasting to obtain calcium oxide at 800 DEG C.
Embodiment 2
Magnesia is added into wood vinegar, stirs evenly at room temperature, reacts 2 hours, makes its pH value 8.0.Filtering removal
Insoluble matter obtains dark brown wood vinegar conversion fluid.2g magnesia, which is added, into 250mL wood vinegar conversion fluid (is equivalent to 8g/
L), and it is stirred, measuring its pH value is 10.0.The wood vinegar conversion fluid upward obtained is passed through ozone, is sent out by ozone
Ozone and oxygen mixed gas that device generates are given birth to, wherein O3Concentration is 100mg/L, flow velocity 500mL/min, and the mixed gas is logical
The SPG membrane continuous bubbling of reactor bottom is crossed into wood vinegar conversion fluid.After the completion of reacting 4h decoloration, wood vinegar is tested
Conversion fluid pH value is 7.8, close to neutrality, directly obtains magnesium acetate aqueous solution by filtering, is further obtained by spray drying
Close to the magnesium acetate solid powder of white.Obtained solid sediment is filtered, is washed, it is dry, it is roasted at 800 DEG C
Magnesia.
Embodiment 3
Calcium hydroxide is added into wood vinegar, stirs evenly at room temperature, reacts 1 hour, makes its pH value 7.0.It filters off
Except insoluble matter, dark brown wood vinegar conversion fluid is obtained.Into 250mL wood vinegar conversion fluid plus 2.5g calcium hydroxide (is equivalent to
10g/L), it and is stirred, measuring its pH value is 10.8.The wood vinegar conversion fluid upward obtained is passed through ozone, is by smelly
The ozone and oxygen mixed gas that Oxygen Generator generates, wherein O3Concentration is 90mg/L, and the porous for passing through reactor bottom
Glass film continuous bubbling is into wood vinegar conversion fluid, flow velocity 400mL/min, after the completion of reaction 3h decoloration, test wood vinegar conversion
Liquid pH value is 7.5, close to neutrality, directly obtains acetic acid calcium saline solution by filtering, is further connect by spray drying
The calcium acetate solid powder of near-white.Obtained solid sediment is filtered to be washed, it is dry, calcium oxide is roasted to obtain at 800 DEG C.
Embodiment 4
Magnesium hydroxide is added into wood vinegar, stirs evenly at room temperature, reacts 1.5 hours, makes its pH value 7.5.Filtering
Insoluble matter is removed, dark brown wood vinegar conversion fluid is obtained.Into 250mL wood vinegar conversion fluid plus 0.5g magnesium hydroxide (is equivalent to
2g/L), it and is stirred, measuring its pH value is 8.1.The wood vinegar conversion fluid upward obtained is passed through ozone, is by ozone
The ozone and oxygen mixed gas that generator generates, wherein O3Concentration is 120mg/L, and the cellular glass for passing through reactor bottom
Film continuous bubbling is into wood vinegar conversion fluid, flow velocity 300mL/min, after the completion of reaction 5h decoloration, tests wood vinegar conversion fluid
PH value is 6.2, and it is neutrality that magnesium hydroxide, which is added, and adjusts wood vinegar conversion fluid pH value, obtains acetic acid magnesium salt solution by filtering,
Further obtain approaching the magnesium acetate solid powder of white by spray drying.Obtained solid sediment is filtered to be washed,
It is dry, magnesia is roasted to obtain at 800 DEG C.
Embodiment 5 (comparison example)
Its operation is substantially same as Example 1, and only obtaining dark brown wood vinegar conversion fluid pH value is 7.5, and oxidation is not added
The directly logical ozone of calcium.
The absorbance value for choosing 290 and 500nm respectively changes (A/A0), to compare catalytic degradation decolorizing efficiency.Wherein A0For
Absorbance value before degradation reaction, A are absorbance value during degradation reaction.It the results are shown in Table 1.
It can be seen that it is obvious to be separately added into calcium oxide, magnesia, calcium hydroxide and magnesium hydroxide degradation effect in example 1-4
Better than comparison example 5.These basic catalysts promote ozone to be converted into the stronger hydroxyl radical free radical of oxidisability, make organic conjugate body
Unsaturated bond (the aromatic radical or conjugated double bond) fracture of chromophoric group generates the aldehyde or acid of small-molecular-weight in system, generates low molecule
The organic matter of amount, since the deeper big conjugated system of color is destroyed, so that water body chroma be made to significantly reduce.Meanwhile it being catalyzed
Ozonisation is the process being constantly acidified, and calcium oxide, magnesia, calcium hydroxide and magnesium hydroxide provide alkaline solution ring
Border is conducive to the generation of hydroxyl radical free radical, accelerates the rate of decomposing organic matter.
Table 1
Embodiment 6
Magnesia is added into wood vinegar, stirs evenly at room temperature, reacts 2 hours, makes its pH value 7.5.Filtering removal
Insoluble matter obtains dark brown wood vinegar conversion fluid.3g magnesia (being equivalent to 3g/L) is added to the wood vinegar conversion fluid of 1L, goes forward side by side
Row stirring, measuring its pH value is 9.0.The wood vinegar conversion fluid upward obtained is passed through ozone, is generated by ozone generator
Ozone and oxygen mixed gas, wherein O3Concentration is 100mg/L, flow velocity 1000mL/min, which passes through reaction
Device bottom continuous bubbling is into wood vinegar conversion fluid.In decoloration acidization, the magnesia is supplemented, wood vinegar conversion fluid is made
PH is maintained at 8 ± 0.5, after the completion of reaction 4h decoloration, magnesium acetate aqueous solution is obtained by filtering, further by being spray-dried
To the magnesium acetate solid powder close to white.Obtained solid sediment is filtered, is washed, it is dry, it is roasted at 800 DEG C
Obtain magnesia.Through detecting, containing 4.04% acetic acid wood vinegar after catalytic ozonation decolourizes, acetate 4.78%,
Yield is 118%, the reason is that some larger molecular organics are degraded to acetate, increases the content of magnesium acetate.
Ether is carried out to the wood vinegar in embodiment 6, wood vinegar conversion fluid and catalytic ozonation degradation destainer respectively
Extraction, and GC-MS (gas chromatography-mass spectrography) analysis is carried out to organic phase.Its result is specific as follows: Fig. 4 and Fig. 5 are respectively
The TIC of the extraction organic phase of raw material wood vinegar and wood vinegar conversion fluid schemes.As seen from the figure, mainly organic as wood vinegar in Fig. 4
The acetic acid of ingredient disappears in Fig. 5.Illustrate that the acetic acid in wood vinegar has been completely converted into acetate ion and has entered water phase.And benzene
The organic principles such as phenols are largely still present in the extraction phase of wood vinegar conversion fluid (no bleaching) organic matter.When wood vinegar turns
Change liquid after O3 catalytic oxidation is decolourized 4 hours, extraction organic phase carries out GC-MS analysis, as shown in Figure 6, it can be seen that big point
The organic matter of son is small organic molecule by catalytic ozonation degradation.
Claims (3)
1. a kind of be used for O3 catalytic oxidation method the method that wood vinegar decolourizes and prepares calcium acetate magnesium salt, it is characterised in that: tool
Steps are as follows for body:
1) solid alkaline object is added into wood vinegar, it includes calcium or the hydroxide of magnesium oxide or calcium or magnesium, at room temperature
It stirs evenly, reacts 1-2 hours, make its pH value in 7-8；
2) filtering removal insoluble matter, obtains dark brown wood vinegar conversion fluid；
3) solid alkaline object described in step 1, additional amount 2-10g/L are added into wood vinegar conversion fluid, and are stirred,
Make pH=8-11；
4) it is passed through ozone to the wood vinegar conversion fluid that step 3 obtains, is the mixed gas generated by ozone generator, the mixing
Gas is the gaseous mixture of ozone and oxygen, wherein O3Concentration is 90-120mg/L, flow velocity 200-1000mL/min, reacts 3-
5h；
5) if wood vinegar conversion fluid pH value is lower than 7 after the completion of decolourizing, the solid alkaline object can be added, adjust wood vinegar conversion
Liquid pH value obtains low-carbon calcium magnesium carboxylate aqueous solution, is further obtained by spray drying close to white close to neutrality by filtering
The low-carbon calcium magnesium carboxylate solid powder based on calcium acetate magnesium salt of color；
6) solid sediment for filtering out step 5 washs, dry, roasts to obtain calcium oxide or magnesia at 800 DEG C.
2. according to claim 1 be used for O3 catalytic oxidation method the side that wood vinegar decolourizes and prepares calcium acetate magnesium salt
Method, it is characterised in that: in oxidative degradation decolorization, solid alkaline object described in step 1 is continuously replenished, makes wood vinegar conversion fluid
PH is maintained at 8 ± 0.5.
3. according to claim 1 be used for O3 catalytic oxidation method the side that wood vinegar decolourizes and prepares calcium acetate magnesium salt
Method, it is characterised in that: mixed gas is turned by the SPG membrane continuous bubbling of reactor bottom to the wood vinegar that step 3 obtains
Change in liquid.
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| CN112251250A (en) * | 2020-10-13 | 2021-01-22 | 海泉风雷新能源发电股份有限公司 | Rice hull vinegar liquid decoking and decoloring process method |
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