CN112174297A - Environment-friendly process for preparing composite carbon source by adopting alkaline crude glycerol - Google Patents
Environment-friendly process for preparing composite carbon source by adopting alkaline crude glycerol Download PDFInfo
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- CN112174297A CN112174297A CN202011021620.5A CN202011021620A CN112174297A CN 112174297 A CN112174297 A CN 112174297A CN 202011021620 A CN202011021620 A CN 202011021620A CN 112174297 A CN112174297 A CN 112174297A
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 412
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000004519 grease Substances 0.000 claims abstract description 39
- 239000003225 biodiesel Substances 0.000 claims abstract description 30
- 239000000344 soap Substances 0.000 claims abstract description 28
- 239000010865 sewage Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 15
- -1 further Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000006386 neutralization reaction Methods 0.000 claims description 18
- 150000007524 organic acids Chemical class 0.000 claims description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 239000006227 byproduct Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 235000011054 acetic acid Nutrition 0.000 claims description 7
- 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 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 9
- 235000011187 glycerol Nutrition 0.000 description 120
- 239000000047 product Substances 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000001632 sodium acetate Substances 0.000 description 10
- 235000017281 sodium acetate Nutrition 0.000 description 10
- 238000007670 refining Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 150000004702 methyl esters Chemical class 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 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 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GFEWRKPOYXKQKX-UHFFFAOYSA-I [C+4].C(C)(=O)[O-].[Na+].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] Chemical compound [C+4].C(C)(=O)[O-].[Na+].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] GFEWRKPOYXKQKX-UHFFFAOYSA-I 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229940040102 levulinic acid Drugs 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 240000001829 Catharanthus roseus Species 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000304337 Cuminum cyminum Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 239000000159 acid neutralizing agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
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- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an environment-friendly process for preparing a composite carbon source by using alkaline crude glycerol, which is characterized in that the alkaline crude glycerol is used as a raw material, organic micromolecular acid is used for neutralizing soap in the alkaline crude glycerol, further, grease in the glycerol is separated, the grease obtained by separation is completely recycled as a biodiesel raw material, the glycerol obtained by separation is used as a sewage treatment composite carbon source, the resource is fully utilized by 100 percent, no pollution is caused, and the economic benefit and the social benefit are very obvious.
Description
Technical Field
The invention belongs to the technical field of glycerol refining, and particularly relates to an environment-friendly process for preparing a composite carbon source by adopting alkaline crude glycerol.
Background
Before 2000, glycerol was mainly derived from oil saponification worldwide and therefore expensive, as exemplified in 1997, where the market price of glycerol was about $ 1700/ton (at that time $ 1 =8.28 RMB), and therefore there was a certain amount of synthetic glycerol, but the production and market were small, where the global glycerol market capacity was 75 million tons.
After 2000 years, the global biodiesel industry is rapidly developed, and in 2008, the global biodiesel yield reaches nearly 1000 ten thousand tons, and reaches 4000 ten thousand tons by 2019, which is estimated to reach 4400 ten thousand tons in 2020, and the corresponding glycerol is about 440 ten thousand tons/year, while the corresponding crude glycerol with the content of 80-85% can reach about 550 ten thousand tons/year; the vigorous development of biodiesel drives and changes the market pattern of glycerin, the price of glycerin is greatly reduced, the price of refined glycerin is about 5000 yuan RMB/ton at present, the price of unrefined crude glycerin is lower, the average price of 85% alkaline glycerin imported in China in 2019 is less than 1700 yuan RMB/ton, and due to the rapid development of the biodiesel industry, the application and development of glycerin are delayed, and the glycerin once becomes a lost product, so that a new application market for developing the glycerin even becomes the key for the smooth development of the biodiesel industry.
Due to the substantial reduction of the price of the glycerol and the development of the international and domestic biodiesel industry, the deep processing of the glycerol in China is gradually deepened, the epichlorohydrin taking the glycerol as the raw material is greatly developed at present, the capacity reaches about 85 ten thousand tons/year, the import quantity of the glycerol is driven to be greatly increased, and the import quantity in 2019 reaches 127 ten thousand tons, which is expected to be further increased.
The biggest bottleneck in the development of the glycerol application market is the glycerol refining process, most of the existing glycerol refining and deep processing technologies are traditional technologies, crude glycerol can be used as a downstream raw material after being subjected to the steps of neutralization, dehydration, decoloration, desalination and vacuum rectification refining, certain pollution can be generated in the crude glycerol refining process, and meanwhile, the cost is increased to limit the expansion of the glycerol application market, so that a resource full-utilization path which is more consistent with atomic economy needs to be actively searched.
With the increasing importance of the country on environmental protection and the increasing of the sewage discharge standard of sewage treatment plants, the requirements of various aspects on sewage treatment are continuously improved. The first grade A discharge standard of pollutants in the urban sewage treatment plant at present is chemical oxygen demand (COD: 50 mg/L), total nitrogen (TN: 15 mg/L, wherein ammonia nitrogen is 5 mg/L) and total phosphorus (TP: 0.5 mg/L). In some areas with higher environmental requirements, the TN content is below 10 mg/L. However, according to the environmental quality standard of surface water, the COD of the V-type water is 40 mg/L, TN and ammonia nitrogen are both 2.0 mg/L, and TP is 0.2 mg/L, that is, after effluent meeting the first-level A discharge standard of a sewage treatment plant enters a river channel to become surface water, the COD is continuously degraded by relying on the self-purification capacity of the river channel, and nitrogen and phosphorus are further removed, so that the water quality of the V-type water can be achieved. The problem of insufficient carbon source exists in the sewage treatment process of a sewage treatment plant or the effluent self-purification process of the sewage treatment plant, and the removal of nitrogen and phosphorus is difficult to a certain extent, so that the external carbon source becomes an important method for improving the sewage treatment efficiency and the self-purification capacity of a river channel, and the currently commonly used external carbon source comprises glycerol, sodium acetate, acetic acid, methanol, ethanol, glucose and the like.
The existing literature proves that glycerol is a high-quality carbon source component, and the results of underground water nitrate removal tests carried out by taking the glycerol as a carbon source, such as the cummins and the like, show that denitrification strains are added into underground water added with the carbon source, so that denitrification reaction can be rapidly started, nitrate can be efficiently removed, and the removal rate can reach more than 97.7%. Summer snow and the like research the efficiency of glycerol as a denitrification phosphorus removal carbon source, and the research shows that the glycerol can be used as the phosphorus removal carbon source of a denitrification process, and the phosphorus removal efficiency can reach 79.2%.
The alkaline crude glycerol contains soap, methyl ester, a small amount of grease, a small amount of methanol, a small amount of water and glycerol, and although the methyl ester, the grease and the glycerol are not soluble, the alkaline crude glycerol is in an emulsified state due to the soap, for example, the separation of the methyl ester, the grease and the glycerol is realized by acidification demulsification; forming fatty acid, fatty acid methyl ester, grease, trace methanol, neutralizing water, neutralizing salt and glycerol after acidification; fatty acid, fatty acid methyl ester and grease form upper layer mixed oil which can be directly used as biodiesel raw material, and the lower layer is mixed solution of trace methanol, water, salt and glycerol; the traditional process adopts hydrochloric acid, sulfuric acid or phosphoric acid for neutralization, so that the composition of upper layer mixed oil is not influenced, the upper layer mixed oil can also be used as a biodiesel raw material, but the lower layer salt is hydrochloride, sulfate or phosphate, the utilization value is hardly high, the application of glycerol is influenced, and the lower layer salt must be removed.
The patent application with publication number CN101058528A discloses a method for separating glycerol, which introduces a method for refining, separating and purifying glycerol, wherein hydrochloric acid and ferric trichloride are added for processing, and the obtained glycerol can be used as a carbon source only by resin treatment.
The patent application with the publication number of CN 104262098A discloses a comprehensive utilization method of crude glycerol as a biodiesel byproduct, wherein the introduced glycerol refining is 'waste methanol acid liquor neutralization', namely, the neutralization is carried out by using self-produced methanol containing sulfate, so that the obtained glycerol contains sulfate and can be used as a carbon source only after resin desalting and vacuum rectification treatment.
Patent application No. CN109179650A discloses a high-efficiency biological composite carbon source and a preparation method thereof, and describes a composite carbon source formula which contains crude glycerol components, but the patent application does not describe the source and content of 35-45% of basic crude glycerol.
The patent application with publication number CN109721471A discloses a method for purifying glycerin from by-products in the production of biodiesel, and the technical scheme is that the glycerin is purified through methanol dilution, alkali neutralization, solvent (insoluble in glycerin) extraction, distillation, water dilution, resin desalination, vacuum dehydration and vacuum distillation.
The patent application with publication number CN 110818079A discloses a biological active carbon source for sewage treatment and a preparation method thereof, and introduces raw materials comprising the following components in parts by weight: 30-35 parts of polyhydric alcohol, 10-20 parts of chitin, 0.5-1.5 parts of vitamin, 3-6 parts of glucose, 20-22 parts of crude glycerol, 2-5 parts of strain and 20-25.5 parts of deionized water.
In summary, the prior art glycerol purification and refining method must be acidified by hydrochloric acid, sulfuric acid or phosphoric acid, and then crude glycerol or refined glycerol containing no chloride ions can be obtained after resin desalting, vacuum dehydration, vacuum distillation and other processes, so that the method can be used for carbon sources; secondly, the existing composite carbon source produced by using the 'crude glycerol' has no clear quality index and raw material source of the 'crude glycerol'.
The byproduct crude glycerol in the existing biodiesel industry is from an alkali catalysis process link, and the main components of the byproduct crude glycerol are methyl ester, methanol, soap, glycerol and other oily impurities; carbon source products have high requirements on oil content and chloride ion content, the purification of the crude glycerol needs neutralization of soap, and the problem needs to be solved by selecting acid for neutralizing the soap, so that the hydrochloric acid is the first option in the prior art, and the carbon source product has the advantages of low cost, small using amount and good oil removal effect; sulfuric acid is selected as a second option, and the method has the advantages that the sulfuric acid is used as an esterification catalyst in a biodiesel factory, and the part of acid is directly used for neutralization, so that comprehensive utilization of resources is realized; however, the glycerol generated in the method contains chloride ions and sulfate radicals, and is not suitable to be directly used as a carbon source, but is at least limited to be used as the carbon source, so that the selection of a novel acid neutralizing agent with wide source, low price and good neutralizing and oil removing effects is the primary problem of realizing the comprehensive utilization of the biodiesel byproduct crude glycerol resource.
Disclosure of Invention
In order to overcome the technical problems in the prior art, the invention aims to provide an environment-friendly process for preparing a composite carbon source by adopting alkaline crude glycerol, which has the advantages of high utilization rate of the crude glycerol, environmental protection and no pollution.
The environment-friendly process for preparing the composite carbon source by adopting the alkaline crude glycerol provided by the invention is characterized in that the alkaline crude glycerol is used as a raw material, the soap in the alkaline crude glycerol is neutralized by adopting the organic micromolecular acid, the grease in the glycerol is further separated, and the grease obtained by separation is completely recycled as the raw material of the biodiesel.
The micromolecular organic acid is any one or combination of several of formic acid, acetic acid, propionic acid, oxalic acid, citric acid, lactic acid and adipic acid.
Further, the small molecular organic acid is preferably any one or a combination of several of oxalic acid, acetic acid, formic acid and citric acid.
The organic small molecular acid is an organic acid with any carbon chain less than or equal to 3.
The organic small molecule acid comprises levulinic acid.
The soap neutralization reaction in the neutralized alkaline crude glycerin is performed under low pressure.
Further, the neutralization reaction is carried out at a pressure of 0.1 to 1.6 MPa.
The neutralization reaction is carried out at a temperature higher than the azeotropic point of the mixed liquid of the small molecular acid, the glycerol, the water and the grease.
Further, the neutralization reaction temperature is carried out at 70 to 150 ℃.
Further, the neutralization reaction temperature is carried out at 100 to 150 ℃.
The alkaline crude glycerol is a byproduct of biodiesel, and contains soap and grease.
The total content of soap and grease in the alkaline crude glycerol is 20-45%.
Further, the total content of soap and grease in the alkaline crude glycerol is 35-45%.
Further, the total content of soap and grease in the alkaline crude glycerol is 40%.
The glycerol layer after oil separation is the sewage treatment nutrient carbon source, and the components of the glycerol layer are a mixture of glycerol, organic acid salt, water and trace methanol.
The environment-friendly process for preparing the composite carbon source by adopting the alkaline crude glycerol has the advantages that the limit of the traditional glycerol refining process is broken through, the soap in the alkaline crude glycerol is neutralized by selecting the organic micromolecule acid, thus, the mixture of glycerol, potassium (sodium) X-acid and water is directly generated, chloride ions and sulfate radicals are not contained, the upper layer grease is recycled as the raw material of the biodiesel, 100 percent of comprehensive utilization of alkaline crude glycerol resources is realized, no wastewater is generated, and more importantly, the added micromolecular organic acid increases the production cost, but the cost increase and surplus are completely offset by the sale of carbon source products, so that the environment protection and profit increase are realized, the technical route breaks through the strange circle of 'environment-friendly and not profitable' or 'environment-friendly and not profitable' of most environment-friendly products in China, and realizes the purposes of environment protection and profit harvest.
Drawings
FIG. 1 is a graph showing the effect of carbon source production according to an embodiment of the present invention;
FIG. 2 is a diagram of the carbon source product composition of an example of the present invention;
Detailed Description
The following will explain the environmental protection process for preparing composite carbon source by using alkaline crude glycerol in detail with reference to the examples.
Examples
In the environment-friendly process for preparing the composite carbon source by using the alkaline crude glycerol, the alkaline crude glycerol is used as a raw material, the soap in the alkaline crude glycerol is neutralized by using the organic small molecular acid, the grease in the glycerol is further separated, and the grease obtained by separation is completely recycled as the biodiesel raw material.
The micromolecular organic acid is any one or combination of several of formic acid, acetic acid, propionic acid, oxalic acid, citric acid, lactic acid and adipic acid.
The organic small molecular acid is an organic acid with any carbon chain less than or equal to 3.
The organic small molecule acid comprises levulinic acid.
The soap neutralization reaction in the neutralized alkaline crude glycerin is performed under low pressure.
Further, the neutralization reaction is carried out at a pressure of 0.1 to 1.6 MPa.
The neutralization reaction is carried out at a temperature higher than the azeotropic point of the mixed liquid of the small molecular acid, the glycerol, the water and the grease.
Further, the neutralization reaction temperature is carried out at 100 to 150 ℃.
The alkaline crude glycerol is a byproduct of biodiesel, and the soap-containing alkaline crude glycerol contains glycerol, soap and grease, wherein the grease mainly comprises fatty glyceride and fatty methyl ester.
The total content of soap and grease in the alkaline crude glycerol is 20-45%, and the balance is glycerol.
Further, the total content of soap and grease in the alkaline crude glycerol is 40%.
The glycerol layer after oil separation is the sewage treatment nutrient carbon source, and the components of the glycerol layer are a mixture of glycerol, organic acid salt, water and trace methanol.
Glycerin is not mutually soluble with fatty acid, neutral oil (fatty glyceride) and fatty methyl ester, but soap (sodium fatty acid and potassium fatty acid) is an emulsifier, so that a soap-containing alkaline crude glycerin layer is in an emulsified state, after organic acid is added, the sodium fatty acid and potassium fatty acid generate fatty acid and organic acid salt, the emulsified state is broken, and the glycerin is settled at the bottom to form a lower layer and an upper layer because the density of the glycerin is 1.25g/cm3 is greater than the density of the oil and fat of 0.80-0.90 g/cm 3; the glycerol layer is discharged from the lower part of the reactor and is the main component of the sewage treatment nutrient carbon source, the components of the glycerol layer are glycerol, organic acid salt and water, and the upper layer grease is recycled as the raw material of the biodiesel.
The specific operation process is as follows:
1. and (3) detection: the soap content and the oil content of alkaline crude glycerol from biodiesel enterprises are detected in a laboratory, the detection principle is that a sample is dissolved by an organic solvent and then titrated by a hydrochloric acid standard solution, and the calculation formula is as follows:
in the formula: x-soap content (mass percent)
V-volume (ml) of hydrochloric acid standard solution consumed by titration of sample solution
V0Titration of blank solution to volume (ml) of hydrochloric acid standard solution consumed
C-hydrochloric acid Standard solution concentration (mol/L)
m-mass of sample (g)
0.304-mass per millimole of sodium oleate, g/mmol (oil is the mixture, oleic acid is typical).
2. Converting the actual organic acid addition amount according to the selected organic acid molecular weight and soap content, gradually adding the organic acid while stirring, heating to 80-100 ℃, adding and stirring until the pH value is stable at about 5 and does not change, pumping into a settling tank for standing, wherein the lower layer is a carbon source intermediate product containing glycerol, and the upper layer of grease is recovered as a biodiesel production raw material; preparing 20% aqueous solution by using deionized water and potassium hydroxide in advance, adding the aqueous solution into a lower-layer product, and adjusting the pH value to 6-7 to obtain the product containing no chlorine radical carbon source.
The carbon source product is proved to be not a flammable and combustible product through detection, and the material characteristics are as follows:
| physical state | Viscous liquid |
| Colour(s) | Reddish yellow |
| Smell(s) | Sweet and |
| ＰＨ | |
| ５—７ | |
| Freezing point | ＜-30℃ |
| Biotoxicity | Is free of |
| Viscosity of | 80cps |
| Boiling or initial boiling and boiling ranges | Data-free data |
| Flash point | １０８℃ |
| Flammability of | Data-free data |
| Upper and lower explosion and flammability limits | Data-free data |
| Steam pressure | Data-free data |
| Relative steam density | Data-free |
| COD value | |
| 100 ten thousand mg/L | |
| BOD value | 79 ten thousand mg/L |
| Density, relative density | 1.22 |
The content of arsenic, cadmium, iron and lead in the carbon source product is measured by an inductively coupled plasma emission spectrometer through the method of JY/T015-:
test results (unit: mg/kg)
| Test items | Method detection limit | Test results |
| Arsenic (As) | 1 | Not detected out |
| Cadmium (Cd) | 1 | Not detected out |
| Iron | 1 | 12 |
| Lead (II) | 1 | Not detected out |
Remarking: (1) mg/kg = ppm
(2) Undetected (< method detection limit)
Example 1
40 tons of alkaline crude glycerol in a biodiesel factory is added with 2.8 tons of formic acid, 12.8 tons of recovered grease and 4.1 tons of potassium hydroxide, and the pH value is adjusted to obtain 34.1 tons of carbon source products, wherein the glycerol content is 62.20 percent, namely 21.21 tons, the total COD is 95 ten thousand mg/L, the chloride content is 120mg/L, the sulfate radical is 232mg/L, the grease content is 0.45 percent, namely 0.153 tons, and the pH value is 5.84. The upper layer 12.8 tons of grease is used as the raw material of biodiesel.
The application comprises the following steps: when the carbon source product is tested in a Changchun sewage treatment plant, the total nitrogen removal rate is 66.97 percent in 4 hours, the nitric nitrogen removal rate is 74.6 percent, and the TN and nitric nitrogen removal rates of raw water without the carbon source are only 10.4 percent and 12.5 percent after 4 hours,
the data obtained are shown in the following table:
| sample name | COD | Total nitrogen | NO3-N | NO2-N | Ammonia nitrogen | MLSS | MLVSS |
| Raw water | 16 | 9.75 | 8.94 | 0.014 | 0.204 | 4505 | 2735 |
| 1 hour of raw water | —— | 9.04 | 8.27 | 0.012 | —— | —— | —— |
| 2 hours of raw water | —— | 8.96 | 8.26 | 0.011 | —— | —— | —— |
| Raw water for 3 hours | —— | 9.52 | 8.25 | 0.023 | —— | —— | —— |
| 4 hours of raw water | 17 | 8.74 | 7.82 | 0.010 | 0.088 | —— | —— |
| Sodium acetate 1 hour | —— | 3.78 | 3.10 | 0.011 | —— | —— | —— |
| Sodium acetate 2 hours | —— | 2.04 | 1.78 | 0.010 | —— | —— | —— |
| Sodium acetate 3 hours | —— | 0.982 | 0.440 | Not detected out | —— | —— | —— |
| Sodium acetate 4 hours | 29 | 1.96 | 0.245 | 0.005 | 0.178 | —— | —— |
| BWD 1 hour | —— | 9.62 | 8.88 | 0.201 | —— | —— | —— |
| BWD 2 hours | —— | 7.14 | 6.24 | 0.172 | —— | —— | —— |
| BWD 3 hours | —— | 4.88 | 3.97 | 0.387 | —— | —— | —— |
| BWD 4 |
25 | 3.22 | 2.27 | 0.689 | 0.165 | —— | —— |
The unit (mg/L) BWD is the carbon source product obtained by the reaction
Example 2
40 tons of alkaline crude glycerol in a biodiesel factory is added with 3.6 tons of acetic acid, 14.4 tons of recovered grease is added with 2.6 tons of alkali, and the pH value is adjusted to obtain 32.84 tons of carbon source products, wherein the glycerol content is 63.8 percent, namely 20.95 tons, the total COD is 92 ten thousand mg/L, the chloride content is 136mg/L, the sulfate radical content is 226mg/L, the grease content is 0.42 percent, namely 0.138 ton, and the pH value is 6.14.
The application comprises the following steps: the carbon source is applied to a Hohaoyao sewage treatment plant, the COD removal rate is 93.3-97.1%, and the average value is 95.4%; the TN removal rate was 58.8% to 73.4%, and the average value was 65.0%.
The sewage of the sewage treatment plant is a mixture of industrial wastewater and domestic sewage, and the C/N value of the sewage treatment plant is lower. The control experiment was performed on site with two carbon sources, sodium acetate and BWD + carbon source. The results of the validation application with the addition equivalent of sodium acetate of 100 ppm and the addition of BWD + carbon source of 70 ppm are shown in the following table:
as can be seen from the above table, the COD content of the influent water of the sewage plant was between 93-273 mg/L throughout the test period. The concentration of TN is between 29.9 and 43.2 mg/L. Is greatly higher than the first grade A effluent standard of a sewage treatment plant. After the sodium acetate carbon source is added, the removal rate of COD is 85.1-96.8%, and the average value is 92.7%; the removal rate of TN was 38.8% to 73.8%, and the average value was 58.1%. After BWD + carbon source is added, the COD removal rate is 93.3-97.1%, and the average value is 95.4%; the TN removal rate was 58.8% to 73.4%, and the average value was 65.0%. Therefore, the removal rate of the carbon source obtained by the process to COD and TN of the sewage generated by the expensive process is superior to that of the sodium acetate carbon source.
Example 3
20 tons of alkaline crude glycerol in a biodiesel factory, 1.6 tons of citric acid, 7.6 tons of recovered grease, 1.3 tons of alkali and pH value adjustment are carried out to obtain 15.3 tons of carbon source products, wherein the content of glycerol is 63.28 percent, namely 12.66 tons, the total COD is 103 ten thousand mg/L, the content of chloride is 116mg/L, the content of sulfate radical is 232mg/L, the content of grease is 0.62 percent, namely 0.124 ton and the pH value is 5.89.
Example 4
40 tons of alkaline crude glycerol in a biodiesel factory are added with 2.8 tons of oxalic acid, 9.7 tons of recovered grease are added with 1.5 tons of alkali, and the pH value is adjusted to obtain 34.61 tons of carbon source products, wherein the content of glycerol is 62.8 percent, namely 25.12 tons, the total COD is 102 ten thousand mg/L, the content of chloride is 121mg/L, the content of sulfate radical is 220mg/L, the content of grease is 0.48 percent, namely 0.192 tons, and the pH value is 6.34.
The following table is a statistical table of the carbon source products obtained in examples 1-4:
the following table is a statistical table of the carbon source product components obtained in examples 1-4:
the whole process realizes 100% utilization of resources, and generates 0.45% solid waste residues due to filtration and impurity removal, belonging to common solid waste.
Compared with sodium acetate, the carbon source product is used for sewage treatment, the cost of each ton of water is only 50 percent of that of sodium acetate, the effect is slightly excellent, and the evaluation conclusion of the catharanthus roseus sewage treatment plant using the carbon source is shown in the following table:
| class of carbon sources | Carbon source unit price (Yuan/ton) | Reduced tonnage water cost (Yuan/m) | Evaluation (price guide) | |
| Sodium acetate (58%) | 3000 | 0.69 | Height of | |
| BWD+Carbon source 100 million COD | 5000 | 0.30 | Is low in |
All water used in the process is deionized water.
Because the glycerol is a grease carbon source, organic acid suitable for being used as a carbon source is used as a neutralizer, the obtained salt is dissolved in the glycerol and directly used as the carbon source, the advantages of the glycerol as the carbon source are still achieved, the defect of slow start of the glycerol is overcome, more importantly, the process has no pollution, is a brand new research worth referencing in chemical product development, realizes the full utilization of 100 percent of resources and has no pollution, the economic benefit and the social benefit are very obvious, and the process is an optimal technical route for biodiesel alkali byproduct at present.
Claims (9)
1. An environment-friendly process for preparing a composite carbon source by adopting alkaline crude glycerol is characterized by comprising the following steps: the method comprises the steps of neutralizing soap in the alkaline crude glycerol by using organic micromolecular acid and further separating grease in the glycerol, wherein the grease obtained by separation is completely recycled as a biodiesel raw material.
2. The environment-friendly process for preparing a composite carbon source by using alkaline crude glycerol according to claim 1, which is characterized in that: the micromolecular organic acid is any one or combination of several of formic acid, acetic acid, propionic acid, oxalic acid, citric acid, lactic acid and adipic acid.
3. The environment-friendly process for preparing a composite carbon source by using alkaline crude glycerol according to claim 2, wherein: the micromolecular organic acid is preferably any one or a combination of a plurality of oxalic acid, acetic acid, formic acid and citric acid.
4. The environment-friendly process for preparing a composite carbon source by using alkaline crude glycerol according to claim 1, which is characterized in that: the neutralization reaction is carried out at a pressure of from 0.1 to 1.6 MPa.
5. The environment-friendly process for preparing a composite carbon source by using alkaline crude glycerol according to claim 1, which is characterized in that: the neutralization reaction temperature is between 70 ℃ and 150 ℃.
6. The environment-friendly process for preparing a composite carbon source by using alkaline crude glycerol according to claim 1, which is characterized in that: the alkaline crude glycerol is a byproduct of biodiesel, and contains soap and grease.
7. The environment-friendly process for preparing a composite carbon source by using alkaline crude glycerol according to claim 6, which is characterized in that: the total content of soap and grease in the alkaline crude glycerol is 20-45%.
8. The environment-friendly process for preparing a composite carbon source by using alkaline crude glycerol according to claim 7, which is characterized in that: the total content of soap and grease in the alkaline crude glycerol is 40%.
9. The environment-friendly process for preparing a composite carbon source by using alkaline crude glycerol according to claim 1, which is characterized in that: the glycerol layer after oil separation is the sewage treatment composite carbon source, and the components of the glycerol layer are a mixture of glycerol, organic acid salt, water and trace methanol.
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| CN114606271A (en) * | 2022-03-28 | 2022-06-10 | 孙庆伦 | Biological carbon source produced by utilizing industrial glycerol and preparation method and application thereof |
| CN115159693A (en) * | 2022-07-11 | 2022-10-11 | 茂名市泓宇能源科技有限公司 | Process and device for preparing composite carbon source by using biodiesel byproduct |
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