US12122687B2 - Method for nitrogen removal and nitrogen salts recovery using carboxylated cellulose extracted by nitro-oxidation - Google Patents
Method for nitrogen removal and nitrogen salts recovery using carboxylated cellulose extracted by nitro-oxidation Download PDFInfo
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- US12122687B2 US12122687B2 US17/267,683 US201917267683A US12122687B2 US 12122687 B2 US12122687 B2 US 12122687B2 US 201917267683 A US201917267683 A US 201917267683A US 12122687 B2 US12122687 B2 US 12122687B2
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- ammonium
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 56
- 239000001913 cellulose Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 11
- 150000002829 nitrogen Chemical class 0.000 title 1
- 238000011084 recovery Methods 0.000 title 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000003337 fertilizer Substances 0.000 claims abstract description 32
- 239000012535 impurity Substances 0.000 claims abstract description 27
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006227 byproduct Substances 0.000 claims abstract description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 11
- -1 ammonium ions Chemical class 0.000 claims description 10
- 239000002028 Biomass Substances 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 7
- 239000004254 Ammonium phosphate Substances 0.000 claims description 6
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical class [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 claims description 6
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical class [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 claims description 6
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 6
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical class N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- 239000002121 nanofiber Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 229920001410 Microfiber Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000003658 microfiber Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 30
- 238000001179 sorption measurement Methods 0.000 description 17
- 235000019270 ammonium chloride Nutrition 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 150000007942 carboxylates Chemical class 0.000 description 11
- 239000000523 sample Substances 0.000 description 10
- 230000001965 increasing effect Effects 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000005189 flocculation Methods 0.000 description 5
- 229920005610 lignin Polymers 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 229920002488 Hemicellulose Polymers 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 240000000491 Corchorus aestuans Species 0.000 description 2
- 235000011777 Corchorus aestuans Nutrition 0.000 description 2
- 235000010862 Corchorus capsularis Nutrition 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 241001307845 Spinifex Species 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 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 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003283 colorimetric indicator Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940100892 mercury compound Drugs 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002972 pentoses Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- 238000004448 titration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002023 wood 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28023—Fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F7/00—Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
- B01J2220/4831—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton having been subjected to further processing, e.g. paper, cellulose pulp
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
Definitions
- Coagulation and flocculation are processes that may be used as preliminary or intermediate steps in the wastewater treatment process and involve separating solids from the water. Coagulation involves using particles with charges opposite of the suspended solids to neutralize the charges and form an aggregate, i.e., particles sticking together. Flocculation is a gentle mixing process that causes the particles to collide and form larger particles which are easier to separate from the water.
- carboxylated cellulose which is an abundant, natural resource that is renewable and recyclable can be used to remove ammonium and nitrogen-containing impurities from contaminated water.
- the invention relates to a method of treating contaminated water to remove ammonium and nitrogen-containing impurities and recover ammonium salts including the following steps: (1) exposing contaminated water to carboxylated cellulose comprising negatively charged functional groups which aggregate with positively charged ammonium ions and nitrogen containing impurities in water, to form an aggregate and treated water; (2) separating the aggregate from the treated water; and (3) isolating ammonium salts from the aggregate, wherein the contaminated water comprises ammonium, nitrogen-containing impurities, or combinations thereof.
- the ammonium salts are converted into ammonium sulfates, ammonium phosphates, ammonium nitrites, ammonium nitrates, ammonium hydroxide, or combinations thereof.
- the carboxylated cellulose is preferably extracted from a raw or untreated biomass using a nitro-oxidation method. Also, the carboxylated cellulose is preferably in the form of microfibers, nanofibers, or combinations thereof. The carboxylated cellulose is preferably present in a concentration of about 0.05% to about 1% based upon the weight of the contaminated water in step (1) above or step (b) below.
- the negatively charged functional groups preferably include —COO ⁇ , —Cl ⁇ , —Br ⁇ , —I ⁇ , —F ⁇ , —CH 2 COO ⁇ , —SO 4 ⁇ 2 , or combinations thereof.
- the ammonium and nitrogen-containing impurities may be present in the contaminated water in about 1 to about 125 ppm.
- the invention also relates to a method of making a fertilizer or a fertilizer component from contaminated water including the following steps: (a) exposing contaminated water to carboxylated cellulose comprising negatively charged functional groups which aggregate with positively charged ammonium ions and nitrogen containing impurities in water, to form an aggregate and treated water; and (b) isolating the aggregate to provide a fertilizer or fertilizer component.
- the aggregate is processed to isolate ammonium salts to provide a fertilizer component.
- the ammonium salts are converted into ammonium sulfates, ammonium phosphates, ammonium nitrites, ammonium nitrates, ammonium hydroxide, or combinations thereof.
- the aggregate is a slow-release fertilizer.
- the nitrogen and oxygen byproducts produced from the nitro-oxidation method may be converted to nitrate salts and added to the fertilizer or fertilizer component provided in step (b).
- FIG. 1 Schematic of ammonium removal using cellulose nanofibers and recycling of removed ammonium into different fertilizing salts.
- the floc obtained during to the interaction of carboxylated cellulose (e.g. CNF) and ammonium ions from contaminated water can be recycled back to nitrogen containing salts such as ammonium nitrates, ammonium nitrites, ammonium phosphates, and ammonium sulfates. These salts can be used as fertilizer for plant growth.
- CNF carboxylated cellulose
- FIG. 2 Removal of mg of ammonium per gram of carboxylated cellulose nanofibers prepared by the nitro-oxidation approach (NOCNF) shown as mg/g and the initial concentration of ammonium in mg/L.
- NOCNF nitro-oxidation approach
- FIG. 3 Maximum adsorption capacity (q m ) and zeta potential (mV) (red) over NOCNF samples of different Degree of Oxidations.
- FIG. 4 Adsorption capacity of ammonium and zeta potential (red) over different pH conditions.
- FIG. 5 TGA of NOCNF and NOCNF with 125 ppm ammonium shown as (A) weight % over temperature and (B) weight %/min over temperature.
- FIG. 6 FTIR of NOCNF (black), NOCNF with 125 ppm ammonium (red), and ammonium chloride (blue).
- the invention relates to treating contaminated water, typically wastewater, with carboxylated cellulose (e.g., CNF) to remove ammonium and nitrogen-containing impurities.
- carboxylated cellulose e.g., CNF
- Carboxylated cellulose works well for this use because cellulose is an abundant, natural, renewable resource. Additionally, the impurities can be recovered to provide a fertilizer or fertilizer component.
- the first step (1) involves exposing contaminated water to carboxylated cellulose.
- the contaminated water can be any water containing ammonium and nitrogen-containing impurities.
- the ammonium and nitrogen-containing impurities may be present in the contaminated water in about 1 ppm ammonium or greater.
- the contaminated water is wastewater.
- the carboxylated cellulose is preferably extracted from a raw or untreated biomass using the nitro-oxidation method. See Sharma, et al. “Nanocellulose from Spinifex as an Effective Absorbent to Remove Cadmium (II) from Water”, ACS Sustainable Chem. Eng. 2018, 6, 3279-3290.
- the nitro-oxidation method can be applied to any type of biomass from agricultural residuals to wood.
- the biomass may be an underutilized plant source. Examples of the biomass include, but are not limited to, jute, grass, spinifex , etc.
- Nitro-oxidation involves the mixtures of nitric acid and sodium nitrite to produce negatively charged carboxylated cellulose in the form of microfibers and/or nanofibers.
- the negatively charged functional groups include, but are not limited to, —COO ⁇ , —Cl ⁇ , —Br ⁇ , —I ⁇ , —F ⁇ , —SO 4 ⁇ 2 and —CH 2 COO ⁇ .
- Negatively charged functional groups, e.g. —COO ⁇ are present in the carboxylated cellulose where the degree of oxidation is typically in the range of 0.1 to 2.0 mmol/g.
- the negatively charged functional groups can interact with positively charged ammonium ions or nitrogen containing impurities, allowing the cellulose scaffold to form an aggregate.
- the resulting aggregate or floc from charge interactions of carboxylated cellulose and ammonium or nitrogen containing impurities possesses organic elements from cellulose, hemicellulose, and lignin as well as inorganic compounds such as ammonium salts.
- the carboxylated cellulose is preferably added to the contaminated water in a concentration of about 0.05% to about 30% based upon the weight of the contaminated water.
- the carboxylated cellulose is exposed to the contaminated water in any way to effectuate the negatively charged functional groups on the carboxylated cellulose to form an aggregate with the positively charged ammonium ions and nitrogen containing impurities in the water. Exposure may include mechanical mixing, propellers, turbines, etc.
- the duration and conditions, e.g., pH, mixing, and temperature can be determined by a person skilled in the art.
- the carboxylated cellulose may be exposed to the wastewater as would a coagulant or an adsorbent.
- the duration of exposure is any amount of time whereby a significant amount of ammonium ions and nitrogen impurities in the water can form an aggregate with the carboxylate cellulose.
- the exposure time may be about 1 minute to about 72 hours.
- the second step (2) involves separating the treated water from the aggregate. This may be accomplished by methods known in the art such as sedimentation, filtration, etc.
- the aggregate may be treated with concentrated sodium chloride to regenerate the carboxylated cellulose so it may be used again in the contaminated water treating process. While carboxylated cellulose may be regenerated numerous times with concentrated sodium chloride, it will eventually degrade and need to be replaced with fresh carboxylated cellulose.
- Another aspect of the invention relates to a method of treating contaminated water to remove ammonium and nitrogen-containing impurities and to recover ammonium salts.
- the method includes steps (1) and (2) above and the additional step (3) of isolating ammonium salts from the aggregate.
- the ammonium salts can be isolated from the aggregate by any method known in the art. For example, the ammonium salts may be separated from the carboxylated cellulose using sodium chloride. The regenerated carboxylated cellulose may then be used again in the process of step (1) to treat contaminated water.
- the separated ammonium salts may be converted into ammonium sulfates, ammonium phosphates, ammonium nitrites, ammonium nitrates, ammonium hydroxide, or combinations thereof which can be used as fertilizer components.
- Step (a) corresponds to step (1) as described above.
- Step (b) involves isolating the aggregate to provide a fertilizer or fertilizer component.
- the aggregate contains organic elements from cellulose, hemicellulose, and lignin as well as inorganic compounds such as ammonium salts. If the carboxylated cellulose in the aggregate is spent meaning the quality of any regenerated carboxylated cellulose would not be efficient for further removal of ammonium ions and nitrogen containing impurities from wastewater, then the entire aggregate including the cellulose may be used as a fertilizer or fertilizer component.
- the aggregate would function as a slow-release fertilizer because it is biodegradable, non-toxic, and loaded with ammonium. When placed in the soil, the ammonium component may slowly enter the soil and potentially reduce nitrogen rich runoff, by releasing the nitrogen more slowly.
- the cellulose-based adsorbent will further decompose.
- the floc obtained by the neutralization and precipitation of the effluent in the nitro-oxidation process can possess organic elements from xylose, pentose, mannose (hemicellulose) and phenolic rings (lignin), excessive nitrogen and oxygen (from the nitro-oxidation) that can also be converted into the form of nitrate salts to be used as a fertilizer component.
- ISE ammonium ion-selective electrode
- a probe including the ion-selective field-effect transistor (ISEFET) was used to measure the change in voltage using a gate insulator specific to ammonium.
- the probe is quantitatively sensitive to the ammonium concentration ranging from 1 ppm to 1000 ppm.
- the second method used to determine the ammonium concentration included the use of a colorimetric indicator, i.e., Nessler's Reagent/potassium tetraiodomercurate (II).
- the mercury compound was coordinated with ammonium and formed a colored complex, which was subsequently measured using ultraviolet-visible spectroscopy (UV-Vis) at 420 nm.
- UV-Vis ultraviolet-visible spectroscopy
- the Nessler's reagent was quantitatively sensitive to the change of ammonium concentration in the range of 1-10 ppm.
- ammonium solutions were prepared by dissolving ammonium chloride in de-ionized water. Using the initial ammonium concentration ranging from 1-125 ppm, the ammonium removal capacity of CNF was found to exhibit a power function relationship with the equilibrium ammonium concentration.
- FIG. 2 shows the adsorption capacity of NOCNF; on the y-axis mg of ammonium adsorbed per gram of NOCNF (mg/g) over ammonium concentration shown as the equilibrium concentration of the combined NOCNF and ammonium on the x-axis.
- the adsorption dramatically increases until an inflexion point. This is driven by the concentration of ammonium.
- the adsorption follows a Langmuir isotherm, which describes monolayer adsorption. This is in agreement with NOCNF, as all carboxylates groups are on the surface.
- Degree of oxidation is expressed as the amount of oxidized functional groups, in this case carboxylic acid, per mass of product, and can be expressed as mmol of carboxylic acid per gram of NOCNF. If the mechanism of ammonium removal is through interaction with carboxylate groups, one would expect to see some differences in NOCNF with different DOs. From FIG. 2 , NOCNF with different DOs are indicated by the legend ranging from 0.2-1.1 mmol/g. As the DO is increased, removal of ammonium increases. FIG. 3 shows increasing maximum capacity of NOCNF as a function of DO. Furthermore, there seems to be a general linear trend of ammonium removal and DO. This provides good evidence that the carboxylate is the major contributor for ammonium adsorption and that adsorption may be tuned via concentration of carboxylate groups.
- FIG. 3 shows the maximum capacity and respective zeta potential over different DOs of NOCNF.
- Zeta potential is a measure of electrical potential at the electrochemical transition between the charged surface and diffuse layer.
- the average negative potential between the surface ions of NOCNF and surrounding solvent may be attributed to the carboxylate groups on the surface of NOCNF.
- DO yields increasingly negative zeta potential and increasing maximum capacity for ammonium.
- FIG. 4 shows the adsorption capacity of NOCNF as the pH is changed.
- the largest adsorption occurs at a pH value of 6.0, where at an equilibrium concentration of 62.5 mg/L, NOCNF adsorbed 17.8 mg/g.
- the adsorption efficiency decreases as the pH value is either lowered or increased, indicating a slightly acidic solution promotes the adsorption of ammonium onto the surface of NOCNF. This may represent the equilibrium of —COOH and —COO ⁇ , commonly reported for ion exchange resins.
- the carboxylate is protonated, and at a higher pH NOCNF may be degraded, in addition to ammonium being deprotonated.
- the black curve represents NOCNF and red curve NOCNF with 125 ppm adsorbed ammonium.
- NOCNF there is a T onset temperature of degradation at 178° C.
- This initial degradation may come from the anhydroglucuronic acid units, as the carboxylate groups are less stable and provide thermal instability.
- the anhydroglucuronic acid unit degradation results in 21% loss in weight.
- the initial degradation at 178° C. partially shrouds the next degradation peak at 270° C.
- the second degradation results in a weight loss of 31%.
- the degradation at higher temperatures may come from high molecular weight lignin which may be heavily crosslinked.
- the T onset occurs at 120° C. This is the degradation of ammonia.
- the respective 10% weight loss is due to the hydrogel properties of NOCNF. Most of its mass comes from water, which may contain ammonium chloride. Upon drying of the sample, ammonium chloride trapped in the swollen hydrogel is left behind. This is followed by the degradation of anhydroglucuronic acid unit for about 48% weight loss.
- the two peaks in differential TGA may reflect the difference in thermal stability of the carboxylated and uncarboxylated cellulose monomers. After treatment with ammonium, the ammonium may decompose before the carboxylate groups, shifting the degradation point to a slightly higher temperature.
- Elemental analysis was conducted on four samples of NOCNF.
- a sample of NOCNF was compared to samples of NOCNF with the addition ammonium chloride.
- the NOCNF sample had no measurable amount of nitrogen, while the samples with ammonium chloride had increasing amounts of nitrogen which correlated with increasing amount of ammonium chloride added to each sample.
- EA is another qualitative indicator, that ammonium adsorption capacity increases with initial concentration.
- the percentage of carbon ranges from 38.4-41.6%, and generally decreases with increasing nitrogen because relative concentrations of the two tend to be inversely related.
- an NOCNF suspension of 0.1-0.2 wt. % is combined with a solution of ammonium chloride (1-125 ppm) in a 1:1 ratio. It is then thoroughly mixed to ensure good interaction. After one hour, the NOCNF shows gelation, and is centrifuged to ensure complete separation from solution.
- micro sized NOCNF is placed in a filter housing unit. As the wastewater passes through the NOCNF, ammonium is removed by the NOCNF, and water passes through.
- the filter unit keeps the NOCNF in place.
- the filter unit is flexible, and may include trickling filters, sand filters, and textile filters.
- micro sized NOCNF is mixed with wastewater in two stages: rapid mixing and slow mixing. Rapid mixing serves to disperse the NOCNF evenly throughout the wastewater, After rapid mix, a longer period of slow mixing (gentle agitation) is used to promote the growth of NOCNF-ammonium floc (flocculation). After flocculation, the water suspension flows into the sedimentation tanks.
- NOCNF Once the NOCNF is saturated with ammonium, it can be removed and used as a fertilizer, or it may be regenerated for further use. NOCNF functions as an ion exchanger. On its first use, the counter ion exists as sodium. NOCNF has a greater affinity for ammonium than sodium, which is why removal of ammonium is observed. To remove the ammonium, a concentrated solution of sodium chloride must be passed through the NOCNF. This method uses high concentration to overcome the higher affinity. Another method is the use of acids and/or bases. From FIG. 4 , the removal efficiency of NOCNF is intrinsically related to pH. If the pH is sufficiently acidic or basic, NOCNF will lose its surface charge and release ammonium.
- the efficiency of the carboxylated cellulose will decrease due to natural degradation, even after regeneration.
- the carboxylated cellulose is removed from for the filter housing and allowed to dry. Once sufficiently dried, the ammonium loaded carboxylated cellulose is laid and sowed over soil. The ammonium loaded carboxylated cellulose can then slowly release the ammonium into soil and fertilize plants. The carboxylated cellulose will then degrade in the soil. Compared to traditional fertilizer, which is applied at once, the ammonium loaded carboxylated cellulose will release more slowly and decrease nitrogen rich runoff.
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Abstract
Description
TABLE 1 |
Degradation temperatures and respective location. |
High | |||||
molecular | |||||
Glucuronic | weight | ||||
Tonset | Ammonium | acid | D-glucose | lignin | |
Sample | (° C.) | (° C.) | (° C.) | (° C.) | (° C.) |
NOCNF | 165 | — | 238 | 293 | 500 |
NOCNF + | 123 | 204 | 280 | 318 | 505 |
ammonium | |||||
TABLE 2 |
Bond stretches for NOCMF, NOCNF with ammonium |
chloride, and ammonium chloride. |
O—H Stretch | N—H Stretch | C—H Stretch | C═Stretch | |
Sample | (cm−1) | (cm−1) | (cm−1) | (cm−1) |
NOCNF | 3284-3343 | — | 2901 | 1603 |
NOCNF + | 3288-3340 | 3019 | 2901 | 1601 |
Ammonium | ||||
Ammonium | — | 3019 | — | — |
TABLE 3 |
Elemental analysis of NOCNF and NOCNF with |
variable concentrations of ammonium chloride solutions. |
Sample | N (%) | C (%) |
NOCNF | 0.00 | 39.80 |
NOCNF + | 0.09 | 41.60 |
5 ppm NH4 + | ||
NOCNF+ | 0.47 | 39.60 |
25 ppm NH4 + | ||
NOCNF + | 2.17 | 38.40 |
125 ppm NH4 + | ||
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