CN110438164A - A method of dilute sulfuric acid is prepared with sludge containing sulphur based on membrane bioreactor - Google Patents

A method of dilute sulfuric acid is prepared with sludge containing sulphur based on membrane bioreactor Download PDF

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CN110438164A
CN110438164A CN201910143600.6A CN201910143600A CN110438164A CN 110438164 A CN110438164 A CN 110438164A CN 201910143600 A CN201910143600 A CN 201910143600A CN 110438164 A CN110438164 A CN 110438164A
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sulphur
sludge
water
sulfuric acid
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辛宝平
杨依然
田炳阳
王佳
张传友
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Beijing University of Technology
Beijing Institute of Technology BIT
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Abstract

The present invention relates to a kind of oxidation green of sludge organism containing sulphur, it is continuous, efficiently prepare the recycling processing method of dilute sulfuric acid, belong to hazardous solid waste disposal of resources and utilize technical field.The industry problems that cannot be filled and burn the invention aims to thoroughly solve sludge containing sulphur, it is aoxidized using autotrophy sulphur/iron-oxidizing bacteria strain (flora) in the growth of membrane bioreactor middle-high density and high-speed, the resource utilization that the harmlessness disposing and dilute sulfuric acid for completing the high-efficiency desulfurization of sludge containing sulphur are quickly prepared.Flora is resistant to by water-washing pre-treatment and breeding height for highly toxic sludge containing sulphur, sulphur/iron-oxidizing bacteria strain growth activity and oxidation activity is significantly improved, greatly improves desulfuration efficiency and relieving haperacidity rate to the sludge containing sulphur.The dilute sulfuric acid (pH0.75-1.0) of output can be used for the neutralization reaction or the extraction recycling of dangerous waste containing heavy metal/solid waste valuable metal of alkaline solid waste；Desulfurization sulphur sludge then can be used for the production such as brick and tile, roadbed and concrete.

Description

A method of dilute sulfuric acid is prepared with sludge containing sulphur based on membrane bioreactor
Technical field
The present invention relates to a kind of oxidation green of sludge organism containing sulphur, it is continuous, efficiently prepare the recycling treatment of dilute sulfuric acid Method belongs to hazardous solid waste disposal of resources and utilizes technical field.
Background technique
A large amount of sulphur are generated in many energy industries that relate to such as petroleum refining, natural gas extraction, coal gas production and gasification of biomass Change hydrogen.These H2The presence of S not only causes the burn into of equipment and pipeline to be detrimental to health, causes explosion detonation；Its Combustion product oxysulfide will also result in the environmental pollutions such as serious acid mist and haze.Therefore, the removing of hypertoxic hydrogen sulfide gas is All significant challenges for relating to energy industry facing.Currently, hydrogen sulfide gas is absorbed using high capacity adsorbent, then utilized The H that claus reaction or the biochemical reaction of sulphur bacteria will be enriched in solution2S is oxidized to simple substance sulphur and recycles and synchronize reality The regeneration cycle of existing adsorbent.While recycling high-purity simple substance sulphur using adsorbing-oxidising coupling technique, also unavoidably A large amount of low-quality sludge containing sulphur must be generated.These sludge containing sulphur generally comprise various concentration (10%-90%, w/w) Sulphur, and it is a variety of containing dust, soil, grease, organic matter, compound alkali, sulfur elimination, fungicide, antisludging agent, coagulant etc. Substance.Therefore, such sludge peculiar smell weight, poor quality, moisture content are high, cannot function as sulfuric acid manufacture raw material.On the other hand, due to The combustibility of sulphur, sludge containing sulphur are all listed in hazardous waste in countries in the world, the supervision most severe by environmental protection administration.
Currently, the processing disposition of the sludge containing sulphur is one of the problem of solid waste field face.Due to high response sulphur In the presence of the prevailing technology of dangerous waste disposition fills and burn the harmless treatment for being difficult to use in the sludge containing sulphur.In the recent period, green peace Entirely, the removing of economical and efficient, environmental-friendly microbial technique for sulphur in sulfur-containing solid, solid waste and dangerous waste.Wherein, change energy Autotrophy sulphur/iron-oxidizing bacteria strain (flora) receives significant attention, which is given birth to by oxidation sulphur and/or ferrous iron Energy needed for long breeding.Sulphur is converted sulfuric acid by chemautotrophy sulphur/iron-oxidizing bacteria strain (flora) under aerobic condition, with This principle realizes the desulfurization of Containing Sulfur sludge and the synchronized compound of dilute sulfuric acid.But for solid containing sulphur/solid waste biological desulphurization There are problems that two.First, current research concentrates on the condition optimizing of desulfurization efficiency to realize the innoxious of the sludge containing sulphur Disposition, the synchronous biological for not relating to dilute sulfuric acid prepare this resource utilization mode.Second, current research is substantially all It is to be carried out in shaking flask small batch, there is no research and develop the bioreactor realization desulfurization for being suitable for and the scale for producing acid and continuously fortune Row.Therefore, there is very big gap apart from practical application in current research.
Membrane bioreactor combines membrane technology and biological liquid phase reactor, is a kind of novel biological reaction apparatus.Its It is mainly characterized by improve the microorganism concn in reactor by the crown_interception of film to improve biological respinse speed； On the other hand, product and microorganism can be separated by the centrifugation of film, realizes that biology prepares the continuous and scale of product Production.Sulphur sludge will be contained and chemautotrophy sulphur/iron-oxidizing bacteria group is co-located among membrane bioreactor, the withholding function of film Lead to sulphur/iron-oxidizing bacteria group high-density growth and promotes the high-efficiency desulfurization and dilute sulfuric acid (pH0.8- of the sludge containing sulphur in turn 1.0) quickly generate；It is raw for the microorganism in membrane bioreactor that the dilute sulfuric acid of generation is effectively discharged in the separation function of film Suitable and stable external environment is created in long breeding and sulphur oxidation.Microbial oxidation processes based on membrane bioreactor will Ensure that the efficient, continuous of the sludge containing sulphur, green bio desulfurization and the simultaneously prepared recycling treatment of sulfuric acid move towards the industrialization and answer With.
Summary of the invention
The invention aims to thoroughly solve hazardous waste sludge containing sulphur to fill and the industry of incineration disposal hardly possible Topic proposes to aoxidize using sulphur/iron-oxidizing bacteria strain (flora) in the growth of membrane bioreactor middle-high density and high-speed, thus complete The resource utilization quickly prepared at the harmlessness disposing and dilute sulfuric acid of the high-efficiency desulfurization of sludge containing sulphur.
The purpose of the present invention is what is be achieved through the following technical solutions.
A method of dilute sulfuric acid is prepared with sludge containing sulphur based on membrane bioreactor, the specific steps are as follows:
Step 1: the water-washing pre-treatment of the sludge containing sulphur.The moisture percentage in sewage sludge containing sulphur and noxious material of separate sources contain It is very big to measure difference.Depending on sludge levels of toxic substances height and Ecotoxicology size, implement not handle or wash pre- place respectively Reason.Water-washing pre-treatment is washed, 1-4 times by 1: 4-1: 10 (v/w)；Water lotion is river water or tap water or recycled water.Washing Sludge containing sulphur afterwards is spare after filters pressing is realized and is separated by solid-liquid separation.
Step 2: high tolerance sulphur/iron-oxidizing bacteria is selected good strains in the field for seed and is educated.By objects such as ultraviolet light irradiation, microwave radiation and nitrosoguanidines Reason, chemistry and the various sulphur of composite means mutagenesis/iron-oxidizing bacteria strain include Thiobacillus thioxidans, Thiobacillus ferrooxidans and thermophilic iron Hook end spirillum etc.；And tolerable separate sources sludge containing the sulphur toxicity of directive breeding acquisition is tamed by gradient and is with it The high tolerance sulphur/iron-oxidizing bacteria group of uniquely/main energy sources growth.
Step 3: realizing that sludge desulfation containing sulphur and dilute sulfuric acid are discontinuously prepared based on membrane bioreactor biological oxidation
(1) preparing microorganism culture solution.Culture solution includes: KH2PO4, 0.25-2.0g/L；Na2HPO4, 0.25-2.0g/L； KNO3, 0.25-1.0g/L；(NH4)2SO4, 0.25-1.0g/L；MgSO4, 0.1-0.5g/L；CaCl2, 0.05-0.25 g/L；Sulphur Sodium thiosulfate, 4.0~40.0g/L；Sludge containing sulphur or water-washing pre-treatment sample (butt), 20.0~200.0g/L；Pyrite, 1.0~10.0g/L.Solvent is tap water, recycled water or river water, natural ph.
(2) biological desulphurization of the sludge containing sulphur and dilute sulfuric acid interval outlet.To membrane reactor (dischargeable capacity 10-200m3) Middle injection contains the microbial culture medium of sludge (or water-washing pre-treatment), and is inoculated with high antitoxin sulphur/iron-oxidizing bacteria group (1.0%-5%, v/v).In certain temperature (25 DEG C -40 DEG C), aeration (dissolved oxygen 40%-100% saturation degree) and stirring (20- 80 revs/min) service condition under, detection architecture pH, ORP, Fe2+, Fe3+With the variation of bacterial strain concentration, cultivate about 5-25 days PH reduces to 0.75-1.0, Fe afterwards2+Concentration reaches 50-200mg/L, Fe3+Concentration reaches 100-400mg/L, bacterial strain concentration reaches (1.0-4.0)×109/ mL, the self priming pump for opening connection membrane module extract the dilute sulfuric acid of pH 0.75-1.0 or by centrifuge and The separation (50%-75%, v/v) of filter press realization sludge and diluted acid.Inorganic salts culture solution is added among membrane reactor to fill out Fill the outlet open circuit of dilute sulfuric acid solution, second of desulfurization of starting and production acid；Second of acid discharge is carried out after pH reduces to 0.75-1.0. It is recycled with this, the design threshold needed for the sulphur concentration in sludge reaches detoxification.
(3) be up to detoxification threshold value desulfurization sludge discharge, and in lime with acidity therein to a kind of solid waste pH It is required that.The microbial culture medium containing fresh sludge is injected into the membrane bioreactor emptied, and be inoculated with high antitoxin sulphur/ The desulfurization and relieving haperacidity of iron-oxidizing bacteria group progress second batch sludge containing sulphur.
Step 4: realizing that sludge desulfation containing sulphur and sulfuric acid are continuously prepared based on membrane bioreactor biological oxidation
(1) preparing microorganism culture solution.Culture solution includes: KH2PO4, 0.25-2.0g/L；Na2HPO4, 0.25-2.0g/L； KNO3, 0.25-1.0g/L；(NH4)2SO4, 0.25-1.0g/L；MgSO4, 0.1-0.5g/L；CaCl2, 0.05-0.25 g/L；Sulphur Sodium thiosulfate, 4.0~40.0g/L；Sludge containing sulphur or water-washing pre-treatment sample (butt), 20.0~200.0g/L；Pyrite, 1.0~10.0g/L.Solvent is tap water, recycled water or river water, natural ph.
(2) biological desulphurization of the sludge containing sulphur and the continuous outlet of dilute sulfuric acid.To membrane reactor (dischargeable capacity 10-200m3) Middle injection contains the microbial culture medium of sludge (or water-washing pre-treatment), and is inoculated with high antitoxin sulphur/iron-oxidizing bacteria group (1.0%-5%, v/v).In certain temperature (25 DEG C -40 DEG C), aeration (dissolved oxygen 40%-100% saturation degree) and stirring (20- 80 revs/min) service condition under, detection architecture pH, ORP, Fe2+, Fe3+With the variation of bacterial strain concentration, cultivate about 5-25 days PH reduces to 0.75-1.0, Fe afterwards2+Concentration reaches 50-200mg/L, Fe3+Concentration reaches 100-400mg/L, bacterial strain concentration reaches (1.0-4.0)×109/ mL, while opening the intake pump of connection inorganic salts culture liquid storage tank and connecting the self priming pump of membrane module (out Water pump).Water discharge speed is controlled to ensure continuation mode outlet diluted acid pH stable in 0.8-1.0；Inflow and outflow is kept simultaneously Balance with realize diluted acid steady and continuous preparation, prepare daily diluted acid volume be 1.0-4.0 times of reactor dischargeable capacity).It is raw Object desulfurization is significantly lowered with sour efficiency is produced after synchronous relieving haperacidity continuous operation 5-20 days, and sludge sulphur removal rate reaches 85%- 95%.
(3) by membrane module self priming pump, centrifuge or filter press by desulfurization sludge and acid culture solution separation, and lime is used Neutralize the pH requirement of acidity therein to a kind of solid waste.Into the membrane bioreactor emptied, injection is containing the micro- of fresh sludge Bio-culture solution, and be inoculated with high antitoxin sulphur/iron-oxidizing bacteria group and carry out the biological desulphurization of second batch sludge containing sulphur and continuously make Acid.
Beneficial effects of the present invention
1. desulfurization and the system of dilute sulfuric acid that the sulphur based on membrane bioreactor/iron autotrophy bacterial strain synchronously completes the sludge containing sulphur It is standby, realize safe, green, economic, the efficient harmless treatment and resource utilization of hazardous waste sludge containing sulphur.
2. be resistant to flora by water-washing pre-treatment and breeding height for highly toxic sludge containing sulphur, can significantly improve sulphur/ The growth activity and oxidation activity of iron-oxidizing bacteria strain greatly improve desulfuration efficiency and relieving haperacidity rate to the sludge containing sulphur.
3. the dilute sulfuric acid (pH 0.75-1.0) of output Gu can be used for alkaline solid waste neutralisation treatment or dangerous waste containing heavy metal/ Useless valuable metal extracts recycling；Desulfurization sulphur sludge then can be used for the production such as brick and tile, roadbed and concrete.
Detailed description of the invention: in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, Fig. 1 will be to embodiment Or attached drawing needed to be used in the description of the prior art is briefly described.Fig. 1 is that acidophilic microorganism removes sulphur in sulfur-bearing sludge The membrane bioreactor schematic diagram of sulphur generation dilute sulfuric acid.In figure: A, air compressor；B, gas flowmeter；C, pH pops one's head in；D, Dissolved oxygen probe；E, speed reducer；F, feeding port；G, membrane module；H, aeration tube；I, water-bath circulating outlet；J, water-bath recycle into The mouth of a river；K, discharge gate；L, sample tap；M1, diluted acid outlet self priming pump (water outlet)；M2, minimal medium liquid input centrifugal pump (water inlet).
Below with reference to examples of implementation, the present invention is described in detail
Embodiment 1
Inorganic salts culture solution is injected in the membrane bioreactor for being 10 cubes to dischargeable capacity, composition includes KNO3, 0.5g/L； (NH4)2SO4, 0.5g/L；KH2PO4, 0.75g/L；Na3PO4, 0.75g/L；MgSO4, 0.5g/L；CaCl2, 0.1g/ L, tap water are prepared, natural pH.Membrane bioreactor is 4 meters high, the cylindrical tank that 2 meters of internal diameter, and material is carbon steel liner Modeling；Membrane module be made of 30 micro-filtering flat plate films (polytetrafluoroethylene (PTFE), 1750 × 490 × 6 millimeters, 0.2 micron of aperture, monolithic membrane 30 ls/h of clear water flux).The sludge containing sulphur from natural gas extraction industry is put into 10 cubes of inorganic salts culture solutions (sulphur concentration 34.4%, 2000 kilograms of dosage, solid-to-liquid ratio (w/v) 20%) and a small amount of pyrite (100 kilograms of dosage, Gu Liquor ratio (w/v) 1.0%), and it is inoculated with the height comprising Thiobacillus thioxidans, Thiobacillus ferrooxidans and leptospirillum ferriphilum etc. Antitoxin sulphur/iron-oxidizing bacteria group (2.5%, v/v).It is vertical in 34 DEG C of temperature of reactor, 50 revs/min of speed of agitator, aeration quantity 4.5 Under the conditions of side/minute, culture solution pH is down to 1.0, Fe after culture 7 days2+Concentration reaches 120mg/L, Fe3+Concentration reaches 250mg/ L, flora concentration rises to 2.1 × 109/mL.At that time, while the intake pump and junctional membrane for connecting inorganic salts culture liquid storage tank being opened The water outlet pump of component keeps disengaging water balance and controls water discharge speed to be 840 ls/h, outlet diluted acid pH stable 1.0, Preparing diluted acid volume daily is 2 times of reactor dischargeable capacitys.20 days sludge sulphur removal rates of continuous operation are up to 93%, sludge Middle Sulphur Residue concentration is 4.2%, amounts to 1960 kilograms of relieving haperacidity.
Embodiment 2
Inorganic salts culture solution is injected in the membrane bioreactor for being 200 cubes to dischargeable capacity, composition includes KNO3, 0.5g/L； (NH4)2SO4, 0.5g/L；KH2PO4, 0.75g/L；Na3PO4, 0.75g/L；MgSO4, 0.5g/L；CaCl2, 0.1g/ L, tap water are prepared, natural pH.Membrane bioreactor is 6 meters high, the cylindrical tank that 7.2 meters of internal diameter, and material is in carbon steel Lining plastic；Membrane module is made of that (polytetrafluoroethylene (PTFE), 1750 × 490 × 6 millimeters, 0.2 micron of aperture is single 600 micro-filtering flat plate films 30 ls/h of piece film clear water flux).Into 200 cubes of inorganic salts culture solutions, investment contains sulphur from natural gas extraction industry Sludge (sulphur concentration 34.4%, 40.0 tons of dosage, solid-to-liquid ratio (w/v) 20%) and a small amount of pyrite (2.0 tons of dosage, Gu Liquor ratio (w/v) 1.0%), and it is inoculated with the highly resistance comprising Thiobacillus thioxidans, Thiobacillus ferrooxidans and leptospirillum ferriphilum etc. Malicious sulphur/iron-oxidizing bacteria group (2.5%, v/v).34 DEG C of temperature of reactor, 40 revs/min of speed of agitator, 120 cubes of aeration quantity/ Under the conditions of minute, culture solution pH is down to 1.0, Fe after culture 8 days2+Concentration reaches 110mg/L, Fe3+Concentration reach 230mg/L, Flora concentration rises to 2.0 × 109/mL.At that time, while the intake pump and junctional membrane group for connecting inorganic salts culture liquid storage tank being opened The water outlet pump of part keeps disengaging water balance and controls water discharge speed to be 16.0 cubic meters/hour, outlet diluted acid pH stable 1.0, Preparing diluted acid volume daily is 2 times of reactor dischargeable capacitys.20 days sludge sulphur removal rates of continuous operation are up to 91%, sludge Middle Sulphur Residue concentration is 5.2%, amounts to 38.3 tons of relieving haperacidity.
Embodiment 3
Inorganic salts culture solution is injected in the membrane bioreactor for being 10 cubes to dischargeable capacity, composition includes KNO3, 0.5g/L； (NH4)2SO4, 0.5g/L；KH2PO4, 0.75g/L；Na3PO4, 0.75g/L；MgSO4, 0.5g/L；CaCl2, 0.1g/ L, recycled water are prepared, natural pH.Membrane bioreactor is 4.0 meters high, the cylindrical tank that 2.0 meters of internal diameter, and material is in carbon steel Lining plastic；Membrane module be made of 30 micro-filtering flat plate films (Kynoar, 1750 × 490 × 6 millimeters, 0.2 micron of aperture, monolithic 30 ls/h of film clear water flux).Into 10 cubes of inorganic salts culture solutions, investment is dirty containing sulphur from natural gas extraction industry Mud (sulphur concentration 34.4%, 2000 kilograms of dosage, solid-to-liquid ratio (w/v) 20%) and a small amount of pyrite (100 kilograms of dosage, Solid-to-liquid ratio (w/v) 1.0%), and be inoculated with comprising Thiobacillus thioxidans, Thiobacillus ferrooxidans and leptospirillum ferriphilum etc. High antitoxin sulphur/iron-oxidizing bacteria group (2.5%, v/v).In 34 DEG C of temperature of reactor, 50 revs/min of speed of agitator, aeration quantity 4.5 Under the conditions of cube/minute, culture solution pH is down to 1.0, Fe after culture 8 days2+Concentration reaches 130mg/L, Fe3+Concentration reaches 240mg/L, flora concentration rise to 2.0 × 109/mL.At that time, at the same open connection inorganic salts culture liquid storage tank intake pump and The water outlet pump of connection membrane module keeps disengaging water balance and controls water discharge speed to be 830 ls/h, outlet diluted acid pH stable 1.0, i.e., preparing diluted acid volume daily is 2 times of reactor dischargeable capacitys.20 days sludge sulphur removal rates of continuous operation reach 92%, Sulphur Residue concentration is 4.9% in sludge, amounts to 1950 kilograms of relieving haperacidity.
Embodiment 4
Inorganic salts culture solution is injected in the membrane bioreactor for being 10 cubes to dischargeable capacity, composition includes KNO3, 0.5g/L； (NH4)2SO4, 0.5g/L；KH2PO4, 0.75g/L；Na3PO4, 0.75g/L；MgSO4, 0.5g/L；CaCl2, 0.1g/ L, recycled water are prepared, natural pH.Membrane bioreactor is 2.0 meters long, 2.0 meters wide, high 3.0 cube tank bodies, bottom four Angle lining material prevents solid material from accumulating.Tank body material is carbon steel lining plastic；Membrane module is made of (poly- 30 micro-filtering flat plate films Tetrafluoroethene, 1750 × 490 × 6 millimeters, 0.2 micron of aperture, 30 ls/h of monolithic membrane clear water flux).It is inorganic to 10 cubes In salt culture solution investment from natural gas extraction industry sludge containing sulphur (sulphur concentration 34.4%, 2000 kilograms of dosage, Solid-to-liquid ratio (w/v) 20%) and a small amount of pyrite (100 kilograms of dosage, solid-to-liquid ratio (w/v) 1.0%), and be inoculated with comprising oxidation Antitoxin sulphur/iron-oxidizing bacteria the group (2.5%, v/v) of height of sulphur Thiobacillus, Thiobacillus ferrooxidans and leptospirillum ferriphilum etc..In Under the conditions of 34 DEG C of temperature of reactor, 50 revs/min of speed of agitator, 5.0 cube/minute of aeration quantity, culture solution pH after culture 7 days It is down to 1.0, Fe2+Concentration reaches 120mg/L, Fe3+Concentration reaches 230mg/L, flora concentration rises to 2.1 × 109/mL.At that time, The water outlet pump of the intake pump and connection membrane module of opening connection inorganic salts culture liquid storage tank simultaneously keeps disengaging water balance and controls Water discharge speed is 840 ls/h, and for outlet diluted acid pH stable 1.0, i.e., preparing diluted acid volume daily is that 2 times of reactors are effective Volume.20 days sludge sulphur removal rates of continuous operation are up to 93%, and Sulphur Residue concentration is 4.3% in sludge, amount to relieving haperacidity 1960 Kilogram.
Embodiment 5
Inorganic salts culture solution is injected in the membrane bioreactor for being 10 cubes to dischargeable capacity, composition includes KNO3, 0.5g/L； (NH4)2SO4, 0.5g/L；Na3PO4, 1.0g/L；MgSO4, 0.25g/L；CaCl2, 0.05g/L, river water preparation, from Right pH.Membrane bioreactor is 4.0 meters high, the cylindrical tank that 2.0 meters of internal diameter, and material is carbon steel lining plastic；Membrane module is by 30 Piece micro-filtering flat plate film composition (polytetrafluoroethylene (PTFE), 1750 × 490 × 6 millimeters, 0.2 micron of aperture, 30 liters of monolithic membrane clear water flux/ Hour).(the sulphur concentration of sludge containing sulphur from natural gas extraction industry is put into 10 cubes of inorganic salts culture solutions 34.4%, 2000 kilograms of dosage, solid-to-liquid ratio (w/v) 20%) and a small amount of pyrite (100 kilograms of dosage, solid-to-liquid ratio (w/v) 1.0%), and it is inoculated with the antitoxin sulphur/iron of height comprising Thiobacillus thioxidans, Thiobacillus ferrooxidans and leptospirillum ferriphilum etc. It aoxidizes flora (2.5%, v/v).In 34 DEG C of temperature of reactor, 50 revs/min of speed of agitator, 4.5 cube/minute item of aeration quantity Under part, culture solution pH is down to 0.8, Fe after culture 12 days2+Concentration reaches 150mg/L, Fe3+It is dense that concentration reaches 310mg/L, flora Degree rises to 2.1 × 109/mL.At that time, while the intake pump of connection inorganic salts culture liquid storage tank and going out for connection membrane module being opened Water pump keeps disengaging water balance and controls water discharge speed to be 430 ls/h, outlet diluted acid pH stable is made daily 0.8 Standby diluted acid volume is 1 times of reactor dischargeable capacity.25 days sludge sulphur removal rates of continuous operation are up to 94%, and sulphur is residual in sludge Staying concentration is 3.8%, amounts to 1980 kilograms of relieving haperacidity.
Embodiment 6
Inorganic salts culture solution is injected in the membrane bioreactor for being 10 cubes to dischargeable capacity, composition includes KNO3, 0.5g/L； (NH4)2SO4, 0.5g/L；Na3PO4, 1.0g/L；MgSO4, 0.25g/L；CaCl2, 0.05g/L, river water preparation, from Right pH.Membrane bioreactor is 4.0 meters high, the cylindrical tank that 2.0 meters of internal diameter, and material is carbon steel lining plastic；Membrane module is by 30 Piece micro-filtering flat plate film composition (polytetrafluoroethylene (PTFE), 1750 × 490 × 6 millimeters, 0.2 micron of aperture, 30 liters of monolithic membrane clear water flux/ Hour).Into 10 cubes of inorganic salts culture solutions, sludge containing sulphur of the investment from coal gas industry (throw by sulphur concentration 25.5% 2000 kilograms of dosage, solid-to-liquid ratio (w/v) 20%) and a small amount of pyrite (100 kilograms of dosage, solid-to-liquid ratio (w/v) 1.0%), and Height antitoxin sulphur/iron-oxidizing bacteria group of the inoculation comprising Thiobacillus thioxidans, Thiobacillus ferrooxidans and leptospirillum ferriphilum etc. (2.5%, v/v).Under the conditions of 34 DEG C of temperature of reactor, 50 revs/min of speed of agitator, 4.5 cube/minute of aeration quantity, culture Culture solution pH is down to 1.0, Fe after 7 days2+Concentration reaches 120mg/L, Fe3+Concentration reaches 230mg/L, flora concentration rises to 2.1 ×109/mL.At that time, at the same open connection inorganic salts culture liquid storage tank intake pump and connection membrane module water outlet pump keep into Out water balance and control water discharge speed be 830 ls/h, outlet diluted acid pH stable prepares diluted acid volume 1.0 daily For 2 times of reactor dischargeable capacitys.15 days sludge sulphur removal rates of continuous operation are up to 94%, and Sulphur Residue concentration is in sludge 4.6%, amount to 1460 kilograms of relieving haperacidity.

Claims (4)

1. a kind of method for preparing dilute sulfuric acid with sludge containing sulphur based on membrane bioreactor, it is characterised in that:
Step 1: the water-washing pre-treatment of the sludge containing sulphur.The moisture percentage in sewage sludge containing sulphur and levels of toxic substances of separate sources are poor It is very not big.Depending on sludge levels of toxic substances height and Ecotoxicology size, implement not handle respectively or water-washing pre-treatment.Washing Pretreatment is washed, 1-4 times by 1: 4-1: 10 (v/w)；Water lotion is river water or tap water or recycled water.Sulfur-bearing after washing Sulphur sludge is spare after filters pressing is realized and is separated by solid-liquid separation.
Step 2: high tolerance sulphur/iron-oxidizing bacteria is selected good strains in the field for seed and is educated.By physics such as ultraviolet light irradiation, microwave radiation and nitrosoguanidines, change It learns and the various sulphur of composite means mutagenesis/iron-oxidizing bacteria strain includes Thiobacillus thioxidans, Thiobacillus ferrooxidans and thermophilic iron hook end spiral shell Revolve bacterium etc.；And tolerable separate sources sludge containing the sulphur toxicity of directive breeding acquisition is tamed by gradient and is unique/main with it Want high tolerance sulphur/iron-oxidizing bacteria group that the energy is grown.
Step 3: realizing that sludge desulfation containing sulphur and dilute sulfuric acid are discontinuously prepared based on membrane bioreactor biological oxidation
(1) preparing microorganism culture solution.Culture solution includes: KH2PO4, 0.25-2.0g/L；Na2HPO4, 0.25-2.0g/L；KNO3, 0.25-1.0g/L；(NH4)2SO4, 0.25-1.0g/L；MgSO4, 0.1-0.5g/L；CaCl2, 0.05-0.25g/L；Thiosulfuric acid Sodium, 4.0~40.0g/L；Sludge containing sulphur or water-washing pre-treatment sample (butt), 20.0~200.0g/L；Pyrite, 1.0~ 10.0g/L.Solvent is tap water, recycled water or river water, natural ph.
(2) biological desulphurization of the sludge containing sulphur and dilute sulfuric acid interval outlet.To membrane reactor (dischargeable capacity 10-200m3) in injection Microbial culture medium containing sludge (or water-washing pre-treatment), and it is inoculated with high antitoxin sulphur/iron-oxidizing bacteria group (1.0%-5%, v/ v).In certain temperature (25 DEG C -40 DEG C), the operation of aeration (dissolved oxygen 40%-100% saturation degree) and stirring (20-80 revs/min) Under the conditions of, detection architecture pH, ORP, Fe2+, Fe3+With the variation of bacterial strain concentration, pH reduces to 0.75- after culture about 5-25 days 1.0、Fe2+Concentration reaches 50-200mg/L, Fe3+Concentration reaches 100-400mg/L, bacterial strain concentration reaches (1.0-4.0) × 109/ ML, the self priming pump for opening connection membrane module extract the dilute sulfuric acid of pH 0.75-1.0 or realize sludge by centrifuge and filter press With the separation (50%-75%, v/v) of diluted acid.Inorganic salts culture solution is added among membrane reactor to fill the outer of dilute sulfuric acid solution Arrange road, second of desulfurization of starting and production acid；Second of acid discharge is carried out after pH reduces to 0.75-1.0.It is recycled with this, until dirty Design threshold needed for sulphur concentration in mud reaches detoxification.
(3) it is up to the desulfurization sludge discharge of detoxification threshold value, and is required in lime with the pH of acidity therein to a kind of solid waste. The microbial culture medium containing fresh sludge is injected into the membrane bioreactor emptied, and is inoculated with high antitoxin sulphur/iron oxidation The desulfurization and relieving haperacidity of flora progress second batch sludge containing sulphur.
Step 4: realizing that sludge desulfation containing sulphur and sulfuric acid are continuously prepared based on membrane bioreactor biological oxidation
(1) preparing microorganism culture solution.Culture solution includes: KH2PO4, 0.25-2.0g/L；Na2HPO4, 0.25-2.0g/L；KNO3, 0.25-1.0g/L；(NH4)2SO4, 0.25-1.0g/L；MgSO4, 0.1-0.5g/L；CaCl2, 0.05-0.25g/L；Thiosulfuric acid Sodium, 4.0~40.0g/L；Sludge containing sulphur or water-washing pre-treatment sample (butt), 20.0~200.0g/L；Pyrite, 1.0~ 10.0g/L.Solvent is tap water, recycled water or river water, natural ph.
(2) biological desulphurization of the sludge containing sulphur and the continuous outlet of dilute sulfuric acid.To membrane reactor (dischargeable capacity 10-200m3) in injection Microbial culture medium containing sludge (or water-washing pre-treatment), and it is inoculated with high antitoxin sulphur/iron-oxidizing bacteria group (1.0%-5%, v/ v).In certain temperature (25 DEG C -40 DEG C), the operation of aeration (dissolved oxygen 40%-100% saturation degree) and stirring (20-80 revs/min) Under the conditions of, detection architecture pH, ORP, Fe2+, Fe3+With the variation of bacterial strain concentration, pH reduces to 0.75- after culture about 5-25 days 1.0、Fe2+Concentration reaches 50-200mg/L, Fe3+Concentration reaches 100-400mg/L, bacterial strain concentration reaches (1.0-4.0) × 109/ ML, while opening the intake pump of connection inorganic salts culture liquid storage tank and the self priming pump (water outlet pump) of connection membrane module.Control water outlet Flow velocity is to ensure continuation mode outlet diluted acid pH stable in 0.8-1.0；Keep the balance of inflow and outflow dilute to realize simultaneously The steady and continuous preparation of acid, preparing diluted acid volume daily is 1.0-4.0 times of reactor dischargeable capacity).Biological desulphurization is made with synchronous Sour continuous operation produces sour efficiency and significantly lowers after 5-20 days, sludge sulphur removal rate reaches 85%-95%.
(3) it by membrane module self priming pump, centrifuge or filter press by desulfurization sludge and acid culture solution separation, and is neutralized with lime The pH of acidity therein to a kind of solid waste is required.Microorganism training of the injection containing fresh sludge into the membrane bioreactor emptied Nutrient solution, and it is inoculated with high antitoxin sulphur/iron-oxidizing bacteria group progress second batch sludge containing sulphur biological desulphurization and continuous relieving haperacidity.
2. a kind of method that dilute sulfuric acid is prepared with sludge containing sulphur based on membrane bioreactor according to claim 1, Be characterized in that: the sulphur based on membrane bioreactor/iron autotrophy bacterial strain (flora) synchronously complete the sludge containing sulphur desulfurization and dilute sulphur Safe, green, economic, the efficient harmless treatment and resource utilization of hazardous waste sludge containing sulphur are realized in the preparation of acid, The type of film is plate membrane, tubular membrane or hollow-fibre membrane in the membrane bioreactor, and the aperture of film is micro-filtration or nanofiltration, film Material be polytetrafluoroethylene (PTFE), Kynoar, polypropylene, ceramics or other organic and inorganic and composite materials, sulphur/iron autotrophy Bacterial strain (flora) refers to a variety of acidophils including Thiobacillus thioxidans, Thiobacillus ferrooxidans and leptospirillum ferriphilum Strain.
3. a kind of method that dilute sulfuric acid is prepared with sludge containing sulphur based on membrane bioreactor according to claim 1, It is characterized in that: flora being resistant to by water-washing pre-treatment and breeding height for highly toxic sludge containing sulphur, significantly improves sulphur/iron oxygen The growth activity and oxidation activity for changing bacterial strain greatly improve the desulfuration efficiency and relieving haperacidity rate to the sludge containing sulphur, height tolerance bacterium Strain (flora) is by physics, chemistry and composite means mutagenesis such as ultraviolet light irradiation, microwave radiation and nitrosoguanidines and passes through gradient Directive breeding is tamed to obtain.
4. a kind of method that dilute sulfuric acid is prepared with sludge containing sulphur based on membrane bioreactor according to claim 1, It is characterized in that: biological desulphurization and dilute sulphur can be realized for the sludge containing sulphur of separate sources, various concentration and different compositions The synchronous preparation of acid, produced dilute sulfuric acid (pH 0.75-1.0) can be used in alkaline solid waste and/or all kinds of dangerous wastes containing heavy metal/solid waste A variety of Consumptions such as valuable metal extraction recycling；Desulfurization sulphur sludge then can be used for a variety of building materials such as brick and tile, roadbed and concrete Metaplasia produces.
CN201910143600.6A 2019-02-26 2019-02-26 A method of dilute sulfuric acid is prepared with sludge containing sulphur based on membrane bioreactor Pending CN110438164A (en)

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