CN102173546B - System and method for generating methane and synchronously removing heavy metal from heavy metal-containing organic solid wastes - Google Patents
System and method for generating methane and synchronously removing heavy metal from heavy metal-containing organic solid wastes Download PDFInfo
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- CN102173546B CN102173546B CN201110021090A CN201110021090A CN102173546B CN 102173546 B CN102173546 B CN 102173546B CN 201110021090 A CN201110021090 A CN 201110021090A CN 201110021090 A CN201110021090 A CN 201110021090A CN 102173546 B CN102173546 B CN 102173546B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002910 solid waste Substances 0.000 title abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 238000000926 separation method Methods 0.000 claims abstract description 32
- 238000002425 crystallisation Methods 0.000 claims abstract description 30
- 230000008025 crystallization Effects 0.000 claims abstract description 30
- 238000010909 chemical acidification Methods 0.000 claims abstract description 24
- 230000020477 pH reduction Effects 0.000 claims abstract description 24
- 238000002386 leaching Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims description 23
- 238000007599 discharging Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000010815 organic waste Substances 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 239000003814 drug Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 230000029087 digestion Effects 0.000 abstract description 11
- 238000000855 fermentation Methods 0.000 abstract description 4
- 230000004151 fermentation Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000029219 regulation of pH Effects 0.000 abstract 3
- 230000006698 induction Effects 0.000 abstract 1
- 230000001939 inductive effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 210000003608 fece Anatomy 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 244000144972 livestock Species 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 244000144977 poultry Species 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000003895 groundwater pollution Methods 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
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- Treatment Of Sludge (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a system and a method for generating methane and synchronously removing heavy metal from heavy metal-containing organic solid wastes, and belongs to the technical field of the digestion of organic solid wastes. The system comprises a biological acidification reactor, a chemical acidification reactor, a pH regulation reactor, a solid-liquid separation reactor, a crystallization inducing reactor and a methane generating reactor, wherein stirrers are arranged in the biological acidification reactor, the chemical acidification reactor and the pH regulation reactor. The method comprises the following steps of: biological acidification, chemical leaching, pH regulation, solid-liquid separation, crystallization induction, anaerobic fermentation and the like. By the method, the digestion speed of the solid wastes can be improved effectively, the yield of the methane can be increased, and the heavy metal in the wastes can be removed to realize safe agricultural utilization of fermentation residues.
Description
Technical field
The invention belongs to the technical field of organic solid waste digestion, relate in particular to a kind of heavy metal organic solid waste that contains and produce the system and method system and method that methane is removed heavy metal synchronously.
Background technology
At present, be big, the generation regional centralized of organic solid waste generation of representative with feces of livestock and poultry, sewage treatment plant residual mud, a large amount of dischargings possibly cause air, surface water and phreatic pollution, thus be detrimental to health.In addition, and beyond the above-mentioned organic solid waste organic matter removal content height, also contain the heavy metal of higher concentration; The final whereabouts of considering these solid waste is generally farmland or soil; Not treated long-term recurrence soil is except organism, nitrogen, phosphorus can cause soil, beyond the groundwater pollution; Also possibly cause heavy metal accumulation in soil or the underground water, cause all kinds of pollution incidents.Therefore before going back to the field, adopt rational system and method that it is handled, seem very urgent.
Generally adopt anaerobic digestion techniques to handle above-mentioned waste both at home and abroad, the organism materials such as producing biogas, natural pond liquid, natural pond slag of under the effect of anaerobion, degrading.Wherein biogas can be utilized effectively as the energy.Be rich in various nutrient elements such as nitrogen, phosphorus in natural pond liquid, the natural pond slag, can be used as compoiste fertilizer reuse farmland, realize with resource circulation utilization.
But, the Anaerobic Digestion process can only the degradable solid waste in organism, and heavy metal still remains in after Anaerobic Digestion in natural pond liquid, the natural pond slag, has directly influenced the agricultural use security of natural pond liquid, natural pond slag.Simultaneously, the efficient of traditional anaerobic digestion techniques processing organic solid waste also awaits further raising.
Summary of the invention
The objective of the invention is for overcoming the weak point of prior art, a kind of organic solid useless system and method that methane is removed heavy metal synchronously that produces of heavy metal that contains is provided, can effectively improve digestion rate, can remove the heavy metal that contains in the heavy metal organic solid waste simultaneously.
The objective of the invention is to realize through following technical scheme:
A kind of organic solid useless system that methane is removed heavy metal synchronously that produces of heavy metal that contains; Belong to the technical field of organic solid waste digestion, this system comprises biological acidification reactor drum, chemical acidification reactor drum, pH regulator reactor drum, solid-liquid separation reactor drum, induced crystallization reactor drum and methane-producing reactor; Wherein the biological acidification reactor drum connects chemical acidification reactor drum, pH regulator reactor drum, solid-liquid separation reactor drum successively through pipeline and valve; The isolated liquid of solid-liquid separation reactor drum links to each other with the induced crystallization reactor drum through pipeline and valve, and the water outlet of isolated solid of solid-liquid separation reactor drum and induced crystallization reactor drum links to each other with methane-producing reactor through pipeline and valve respectively; Be provided with whisking appliance in said biological acidification reactor drum, chemical acidification reactor drum, the pH regulator reactor drum.
Adopt according to claim 1 that the heavy metal high solids content organic waste that contain of method efficiently produce the method that methane is removed heavy metal synchronously, it is characterized in that this method may further comprise the steps:
1) pending organic solidliquid mixture at first gets into the biological acidification reactor drum and carries out the biological hydrolysis acidifying, stirring frequency 2-5 commentaries on classics/min, and the residence time is 2-3d in this reactor drum, and pH is reached at 4-6;
2) discharging of biological acidification reactor drum gets into the chemical acidification reactor drum, stirring frequency 5-10 commentariess on classics/min, and through the inorganic acid for adjusting pH of interpolation, with pH regulator to 1.5-2; The residence time is 3-13h in this reactor drum, and heavy metal leaching from the organic waste solid phase gets into liquid phase;
3) discharging of chemical acidification reactor drum is regulated the pH value through adding NaOH in the pH regulator reactor drum, and the scope of pH value is 4-7, the about 5-10 commentaries on classics/min of stirring frequency, and the residence time is 0.5-1h in this reactor drum;
4) discharging of pH regulator reactor drum entering solid-liquid separation reactor drum carries out solid-liquid separation; The supernatant that wherein contains heavy metal gets into the induced crystallization reactor drum; Through adding the crystalline deposit medicament, the mol ratio of deposition medicament and heavy metal ion is 1.0-3.0 in the induced crystallization reactor drum; With heavy metal substance in the supernatant and water sepn, make the heavy metal in the liquid phase remove recovery through the crystalline mode;
5) solid of crystallization reactor water outlet and solid-liquid separation generation gets into the methane-producing reactor aerogenesis jointly, residence time 15-25d in crystallization reactor, and the gas of end reaction device, liquid, solid discharging realize safe agricultural use.
The present invention has the following advantages and positive effect:
(1) it is big to have solved digestion such as excess sludge, feces of livestock and poultry, organic waste difficulty, and the problem that gas producing efficiency is low has improved the conversion rate of organic matter of high solids content organic materials.
(2) solve the high problem of organic waste fermentation resistates heavy metal content, realized agriculture safe utilization
(3) promptly realized efficient aerogenesis, again heavy metal obtained reclaiming with the crystalline mode simultaneously to have good environment and economic benefit.
The present invention is applicable to that heavy metal content such as city excess sludge, feces of livestock and poultry are high, the digestion difficulty is big, the high concentration organic material that gas producing efficiency is low; It is high to have solved fermentation residue matter heavy metal content, can't realize the problem of safe agricultural use.
Description of drawings
Fig. 1 produces the synoptic diagram that methane is removed the system and method for heavy metal synchronously for the present invention contains the heavy metal organic solid waste.
Embodiment
A kind of organic solid useless system and method that methane is removed heavy metal synchronously that produces of heavy metal that contains of the present invention is described with reference to the accompanying drawings as follows:
System of the present invention forms as shown in Figure 1, and this system comprises biological acidification reactor drum 1, chemical acidification reactor drum 2, pH regulator reactor drum 3, solid-liquid separation reactor drum 4, induced crystallization reactor drum 5 and methane-producing reactor 6; Wherein biological acidification reactor drum 1 connects chemical acidification reactor drum 2, pH regulator reactor drum 3, solid-liquid separation reactor drum 4 successively through pipeline and valve; Solid-liquid separation reactor drum 4 isolated liquid link to each other with induced crystallization reactor drum 5 through pipeline and valve, and the water outlet of solid-liquid separation reactor drum 4 isolated solids and induced crystallization reactor drum 5 links to each other with methane-producing reactor 6 through pipeline and valve respectively.
Be provided with whisking appliance in said biological acidification reactor drum 1, chemical acidification reactor drum 2, the pH regulator reactor drum 3.
The heavy metal high solids content organic waste that contain above-mentioned among the present invention efficiently produce the method that methane is removed heavy metal synchronously, and its embodiment may further comprise the steps:
1) the organic solidliquid mixture of high solids content (solid holdup 8-12%) at first gets into biological acidification reactor drum 1 and carries out the biological hydrolysis acidifying; The about 2-5 commentaries on classics/min of stirring frequency (minute); In this reactor drum the residence time be 2-3d (my god); Organic waste reach at 4-6 pH under the effect of acidifying microbes (inoculation of reactor start-up stage, or spontaneous cultivation formation in the reactor drum operational process); This process mainly under action of microorganisms, is converted into larger molecular organics small organic molecules such as organic acid.When improving product methane efficient, consume certain basicity, save the dosage of mineral acid in the heavy metal chemical leaching process;
2) discharging of biological acidification reactor drum gets into chemical acidification reactor drum 2 then, and is main through interpolation mineral acid (example hydrochloric acid, nitric acid) adjusting pH in the about 5-10 commentariess on classics/min of stirring frequency, this reactor drum, with pH regulator to 1.5-2; In this reactor drum the residence time be 3-13h (hour), under the effect of mineral acid, heavy metal leaching from the organic waste solid phase gets into liquid phase;
3) discharging of chemical acidification reactor drum is regulated the pH value to fixed value (according to follow-up crystalline needs) through adding NaOH in pH regulator reactor drum 3, and the scope of pH value is 4-7, the about 5-10 commentaries on classics/min of stirring frequency, and the residence time is 0.5-1h in this reactor drum;
4) discharging of pH regulator reactor drum 3 entering solid-liquid separation reactor drum 4 carries out solid-liquid separation; The supernatant that wherein contains heavy metal gets into induced crystallization reactor drum 5; Through adding crystalline deposit medicament (like carbonate, dissolvable sulfide etc.), the mol ratio of deposition medicament and heavy metal ion is 1.0-3.0 in the induced crystallization reactor drum.With heavy metal substance in the supernatant and water sepn, make the heavy metal in the liquid phase remove recovery through the crystalline mode;
5) solid of crystallization reactor water outlet and solid-liquid separation generation gets into methane-producing reactor 6 aerogenesis jointly; Methane-producing reactor adopts the reactor types of CSTR; About 15-25d of the residence time in crystallization reactor, the gas of end reaction device, liquid, solid discharging all can realize safe agricultural use.
A kind of heavy metal organic solid waste that contains of the present invention produces methane and removes the system embodiment of heavy metal synchronously and be:
This system comprises biological acidification reactor drum 1, chemical acidification reactor drum 2, pH regulator reactor drum 3, solid-liquid separation reactor drum 4, induced crystallization reactor drum 5 and methane-producing reactor 6; Wherein biological acidification reactor drum 1 connects chemical acidification reactor drum 2, pH regulator reactor drum 3, solid-liquid separation reactor drum 4 successively through pipeline and valve; Solid-liquid separation reactor drum 4 isolated liquid link to each other with induced crystallization reactor drum 5 through pipeline and valve, and the water outlet of solid-liquid separation reactor drum 4 isolated solids and induced crystallization reactor drum 5 links to each other with methane-producing reactor 6 through pipeline and valve respectively; Wherein, biological acidification reactor drum 1 and methane-producing reactor 6 adopt the product of the structure of reactor form of CSTR.The product of mature technologies such as that said solid-liquid separation reactor drum 4 can adopt is concentrated, dehydration.Said induced crystallization reactor drum 5 adopts the structure formation of fluidized-bed.The container of chemical acidification reactor drum 2 for adopting acid resisting material to process, pH regulator reactor drum 3 is a conventional containers; Be provided with whisking appliance in said biological acidification reactor drum 1, chemical acidification reactor drum 2, the pH regulator reactor drum 3.Chemical acidification reactor drum and pH regulator reactor drum realize that through whisking appliance pH regulator is even.
Adopt the method embodiment that the heavy metal organic solid waste produces methane and removes heavy metal that contains of the foregoing description, may further comprise the steps:
1) the organic solidliquid mixture waste material that contains rate 8% at first gets into the biological acidification reactor drum, and the residence time is 2d, and the about 3 commentaries on classics/min of stirring frequency reach 4.5 pH; Organic waste have reduced the pH value and the basicity of material to a certain extent under the effect of acidifying microbes (spontaneous cultivation forms in the reactor drum operational process);
2) discharging of biological acidification reactor drum gets into the chemical acidification reactor drum, and the about 7 commentaries on classics/min of stirring frequency regulate pH through adding hydrochloric acid, and 2, the residence time is 5h with pH regulator, makes heavy metal leaching from the organic waste solid phase get into liquid phase;
3) discharging of chemical acidification reactor drum is regulated pH value to 6 through adding NaOH in the pH regulator reactor drum, the about 4 commentaries on classics/min of stirring frequency (minute), the residence time is 0.5h;
4) discharging of pH regulator reactor drum 3 entering solid-liquid separation reactor drum carries out supernatant (the liquid solid content should be lower than 1% after the solid-liquid separation) the entering induced crystallization reactor drum that solid-liquid separation wherein contains heavy metal; Through adding yellow soda ash, the mol ratio of yellow soda ash and heavy metal ion is 1.2 in the induced crystallization reactor drum.With heavy metal substance in the supernatant and water sepn, make the heavy metal in the liquid phase remove recovery (heavy metal removing rate can reach 93%) through the crystalline mode;
5) solid of crystallization reactor water outlet and solid-liquid separation generation gets into the methane-producing reactor aerogenesis jointly, about 18d of the residence time, and the methane gas discharging can realize safe agricultural use.
The above; Be merely the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, any technician who is familiar with the present technique field is in the technical scope that the present invention discloses; The variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.
Claims (2)
1. one kind contains the organic solid useless system that methane is removed heavy metal synchronously that produces of heavy metal; It is characterized in that this system comprises biological acidification reactor drum, chemical acidification reactor drum, pH regulator reactor drum, solid-liquid separation reactor drum, induced crystallization reactor drum and methane-producing reactor; Wherein the biological acidification reactor drum connects chemical acidification reactor drum, pH regulator reactor drum, solid-liquid separation reactor drum successively through pipeline and valve; The isolated liquid of solid-liquid separation reactor drum links to each other with the induced crystallization reactor drum through pipeline and valve, and the water outlet of isolated solid of solid-liquid separation reactor drum and induced crystallization reactor drum links to each other with methane-producing reactor through pipeline and valve respectively; Be provided with whisking appliance in said biological acidification reactor drum, chemical acidification reactor drum, the pH regulator reactor drum.
2. that adopts system according to claim 1 contains the organic solid useless method that methane is removed heavy metal synchronously of producing of heavy metal, it is characterized in that this method may further comprise the steps:
1) pending organic solidliquid mixture at first gets into the biological acidification reactor drum and carries out the biological hydrolysis acidifying, stirring frequency 2-5 commentaries on classics/min, and the residence time is 2-3d in this reactor drum, and pH is reached at 4-6;
2) discharging of biological acidification reactor drum gets into the chemical acidification reactor drum, stirring frequency 5-10 commentariess on classics/min, and through the inorganic acid for adjusting pH of interpolation, with pH regulator to 1.5-2; The residence time is 3-13h in this reactor drum, and heavy metal leaching from the organic waste solid phase gets into liquid phase;
3) discharging of chemical acidification reactor drum is regulated the pH value through adding NaOH in the pH regulator reactor drum, and the scope of pH value is 4-7, stirring frequency 5-10 commentaries on classics/min, and the residence time is 0.5-1h in this reactor drum;
4) discharging of pH regulator reactor drum entering solid-liquid separation reactor drum carries out solid-liquid separation; The supernatant that wherein contains heavy metal gets into the induced crystallization reactor drum; Through adding the crystalline deposit medicament, the mol ratio of deposition medicament and heavy metal ion is 1.0-3.0 in the induced crystallization reactor drum; With heavy metal substance in the supernatant and water sepn, make the heavy metal in the liquid phase remove recovery through the crystalline mode;
5) solid of crystallization reactor water outlet and solid-liquid separation generation gets into the methane-producing reactor aerogenesis jointly, residence time 15-25d in crystallization reactor, and the gas of end reaction device, liquid, solid discharging realize safe agricultural use.
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| Title |
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| 刘晓剑."强化水解酸化同步沥滤重金属技术的研究".《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》.2011,(第01期),第3-4、9-10、79-81页，图1-1. |
| 刘晓剑."强化水解酸化同步沥滤重金属技术的研究".《中国优秀硕士学位论文全文数据库(工程科技Ⅰ辑)》.2011,(第01期),第3-4、9-10、79-81页,图1-1. * |
| 熊娅."诱导结晶法去除和回收废水中的重金属".《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》.2010,(第04期),第103-104页，图6-10. |
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