CN108517224A - A method of nutrient nitrogen recycles organic element carbon simultaneously in removing microalgae hydrothermal liquefaction waste water - Google Patents

A method of nutrient nitrogen recycles organic element carbon simultaneously in removing microalgae hydrothermal liquefaction waste water Download PDF

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CN108517224A
CN108517224A CN201810307976.1A CN201810307976A CN108517224A CN 108517224 A CN108517224 A CN 108517224A CN 201810307976 A CN201810307976 A CN 201810307976A CN 108517224 A CN108517224 A CN 108517224A
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reaction
water
hydrothermal liquefaction
temperature
waste water
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CN108517224B (en
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黄艳琴
袁松
庄修政
刘华财
阴秀丽
吴创之
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Guangzhou Institute of Energy Conversion of CAS
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Guangzhou Institute of Energy Conversion of CAS
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/008—Controlling or regulating of liquefaction processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

The invention discloses the methods that nutrient nitrogen in a kind of removing microalgae hydrothermal liquefaction waste water recycles organic element carbon simultaneously, nutrient nitrogen in hydrothermal liquefaction water phase is reduced into nitrogen release by diazo-reaction, water phase that treated is used as the solvent of hydrothermal liquefaction, at high temperature, C and H in hydrothermal liquefaction generate macromolecular product by polymerisation, it is converted into bio oil, the organic elements such as C, H in energy effective recycling raw material improve the economy of technical process.

Description

Nutrient nitrogen recycles organic simultaneously in a kind of removing microalgae hydrothermal liquefaction waste water The method of elemental carbon
Technical field：
The present invention relates to high organic content wastewater treatment and recycling fields, and in particular to a kind of removing microalgae water The method that nutrient nitrogen recycles organic element carbon simultaneously in hydrothermal solution waste water.
Background technology：
Hydrothermal liquefaction is a kind of conversion means of highly effective, it can be directly by high-water content seaweed, sludge, animal excreta Just equal biomass materials Efficient Conversion is the liquid fuels such as bio oil, has without drying, saves the advantages such as energy consumption；But simultaneously A large amount of hydrothermal liquefaction waste water is generated, these waste water are enriched the largely hydrophily organic matter containing C and N, and component is more complicated, and It is had a certain difference with the difference of raw material type and reaction condition.It is rich in water-phase product by taking algal biomass raw material as an example Collected 50% organic C in seaweed, 30% H and 60% nutrient N, in addition to this also contain phosphorus, metal salt etc.；If Direct emission not only leads to serious environmental pollution, can also cause a large amount of energy waste.Therefore, it is necessary to reinforce hydro-thermal liquid The renewable resources for changing waste water utilize, and the economy of hydrothermal liquefaction process is further increased while avoiding environmental pollution.
Currently, being directed to hydrothermal liquefaction waste water not ripe treatment technology.Patent 201210566119.6 is proposed water The water phase generated in hydrothermal solution liquefaction is added as the nutrient solution of both culturing microalgae in cultivating system, in the same of production bio oil Shi Jinhang both culturing microalgaes；Patent 201110008373.X propose a kind of microalgae treated sewage and produce bio-oil system and Method；A kind of method and apparatus using microbiological treatment waste water of patent 201510266963.0 invention, passes through photosynthetic bacteria With the nutrient in microalgae combined recovery waste water；The core of above these types method is all by recycling the battalion in waste water It supports element and carries out both culturing microalgae, the key parameters such as the organic matter concentration in waste water are adjusted by dilution to optimize water treatment effect And bio-fuel is produced, to achieve the purpose that utilization of wastewater resource.But it is important to note that in addition to organic component Outside, a large amount of poisonous and harmful compound is also contained in waste water, in practice it has proved that, these compounds seriously can inhibit algal grown to make Algae yield is very low, ultimately causes that wastewater treatment cycle is very long, and a large amount of waste water timely and effective cannot be handled；Simultaneously because water phase group It is point more complicated, it is difficult to which the method for finding economic and reliable detaches these poisonous and harmful substances from water phase.
In order to fully recycle the organic element in water phase, the economy of process is improved, can water-phase product be subjected to energy Sourceization utilizes：There is researcher to propose that carrying out reformation to water-phase product prepares hydrogen fuel, but this method is just in water phase Hydrogen, a large amount of organic carbon cannot be fully used；Patent 201611095760.0 proposes a kind of high organic content waste water The method of energy again should by high temperature and pressure (600 DEG C) by the gas component that the organic matter transformation in waste water is high added value Method can make full use of the organic element in water phase, but need waste water being heated to higher temperature (far above the overcritical temperature of water Degree), it is relatively high to equipment requirement and secondary energy consumption, meanwhile, it is important to note that being enriched in the nutrient in water phase The reactions such as polymerization/depolymerization can occur at high temperature under high pressure for N, discharge a large amount of NH3、NO2Deng causing environmental pollution.Therefore, having must Develop new hydrothermal liquefaction waste water treatment process.
Invention content：
In order to solve the problems in the prior art, the purpose of the present invention is to and it is insufficient, a kind of removing microalgae hydrothermal liquefaction is provided and is given up The method that nutrient nitrogen recycles organic element carbon simultaneously in water.
The present invention is achieved by the following technical programs：
A method of nutrient nitrogen recycles organic element carbon, the party simultaneously in removing microalgae hydrothermal liquefaction waste water Method includes the following steps：
1) seaweed raw material is placed in reaction kettle, deionized water is added, be uniformly mixed, seal reaction kettle；Under inert atmosphere It is heated to 150-300 DEG C, and keeps reaction 20-60 minutes at this temperature, reaction terminates to be detached after product cooling, extract It takes, bio oil and water-phase product is obtained by filtration；
2) dilution heat of sulfuric acid is added into the water-phase product of step 1) hydrothermal liquefaction, adjusts the pH of solution<2,10 DEG C with Lower addition sodium nitrite solution keeps 20-40min at this temperature by the heated aqueous after reaction to 40-60 DEG C；It is added NaOH or Ba (OH)2, adjust pH and make SO4 2-It precipitates；
3) water phase that step 2) obtains is further used as the solvent of microalgae hydrothermal liquefaction, and reaction temperature is 250-350 DEG C, And reaction 20-60 minutes, isolated bio oil are kept at this temperature.
The present invention is compared with the prior art, advantage is：
1) nutrient nitrogen in hydrothermal liquefaction water phase is reduced into nitrogen release by diazo-reaction, reduced in water phase Total N content removes the eutrophication of hydrothermal liquefaction waste water, reduces the generation of nitrogenous compound during alternative energyization utilizes；
2) water phase that treated is used as the solvent of hydrothermal liquefaction, and at high temperature, the C and H in hydrothermal liquefaction are anti-by polymerizeing Macromolecular product should be generated, bio oil is converted into, the organic elements such as C, H in energy effective recycling raw material improve technique The economy of process.
Description of the drawings：
Fig. 1 is the process flow chart of the present invention.
Specific implementation mode：
It is the further explanation to the present invention below, rather than limiting the invention.
Embodiment 1：
(1) diatom that Shenzhen Daya Gulf is cultivated is chosen, is baked to crush to sieve with 100 mesh sieve, obtains about 150 μm of powder of grain size As raw material for standby；Component analysis is carried out to it：Protein content about 29.60wt%, fat content 8.2wt%, contents of saccharide 26.97wt%, content of ashes 35.23wt%；Elements C, H, N, S content are respectively 31.92wt%, 4.45wt%, 5.22wt% And 1.14wt%.
(2) it weighs 20g raw materials to be added in the reaction kettle of 300ml, and the deionized water that 100ml is added is uniformly mixed, it is close Seal reaction kettle；It opens breather valve and is passed through inert gas argon gas, purge reaction kettle 20min, the air displaced in kettle ensures in kettle For inert atmosphere；300 DEG C are warming up to, and reacts 30min at this temperature；Products therefrom separation, extraction, filtering can be obtained Biological oily product and water-phase product.Biological oily yield is 18.2wt%, wherein C and N content be respectively 73.38wt% and 5.32wt%, calorific value 35.88MJkg-1；Total N and TOC analyses are carried out to water-phase product, find in raw material there are about The C of the N and 40.78wt% of 47.67wt% have been enriched in water phase；
(3) the isolated water phase of 20ml steps (2) is measured, dilute sulfuric acid (0.5mol/L) about 6ml is added, ensures that water phase is molten Liquid is acidic atmosphere；Container equipped with aqueous phase solution is put into ice bath, keeps ice water bath temperature at 10 DEG C hereinafter, slowly dripping Enter NaNO2Solution (0.02mol/L) 20ml, the primary amine during instillation in water phase occur diazo-reaction with sodium nitrite and generate Diazol；It is put into after reaction in water-bath and is heated to 55 DEG C, keep 20-40min at this temperature, during heating not Disconnected to have bubble to emerge, i.e., the N element in water phase is reduced into N2Release；After reaction, NaOH or Ba (OH) is added2, adjust pH And make SO4 2-It precipitates, total N analyses is carried out to raw material, discovery has 44.8% N to be removed；
(4) it weighs 10mg diatom raw materials to be added in reaction kettle, using treated in step (3), aqueous phase solution is molten as reaction Agent is heated to 300 DEG C, and keeps reaction 20-60 minutes at this temperature, finally obtains bio oil, it is found that biological oily yield is 18.54wt%, C and N in bio oil are respectively 74.37wt% and 5.36wt%, calorific value 36.18MJkg-1；It can see Go out, C takes part in the bio oil of polymerisation generation at high temperature in water phase, improves the C content in bio oil, and gained is biological N in oil is not significantly increased.
As can be seen that the technique can effectively remove the nutrient N in water phase, while can also recycle organic in water phase Elements C and H, make it be converted into bio oil, provide the economy of technical process.
Embodiment 2：
Reference implementation example 1, the difference is that:Step (2) is warming up to 150 DEG C, and reacts 60min at this temperature；
Step (3), which is put into after reaction in water-bath, is heated to 40 DEG C, keeps 20-40min at this temperature；Step (4) 10mg diatom raw materials are weighed to be added in reaction kettle, treated in step (3) aqueous phase solution is regard as reaction dissolvent, heats To 250 DEG C, and reaction 20-60 minutes is kept at this temperature.

Claims (1)

1. a kind of method that nutrient nitrogen recycles organic element carbon simultaneously in removing microalgae hydrothermal liquefaction waste water, feature It is, this approach includes the following steps：
1) seaweed raw material is placed in reaction kettle, deionized water is added, be uniformly mixed, seal reaction kettle；It is heated under inert atmosphere To 150-300 DEG C, and reaction 20-60 minutes is kept at this temperature, reaction terminates to be detached after product cooling, extract, mistake Filter obtains bio oil and water-phase product；
2) dilution heat of sulfuric acid is added into the water-phase product of step 1) hydrothermal liquefaction, adjusts the pH of solution<2, add at 10 DEG C or less Enter sodium nitrite solution, by the heated aqueous after reaction to 40-60 DEG C, keeps 20-40min at this temperature；Be added NaOH or Ba(OH)2, adjust pH and make SO4 2-It precipitates；
3) water phase that step 2) obtains is further used as the solvent of microalgae hydrothermal liquefaction, and reaction temperature is 250-350 DEG C, and Reaction 20-60 minutes, isolated bio oil are kept at a temperature of this.
CN201810307976.1A 2018-04-08 2018-04-08 Method for removing nutrient element nitrogen in microalgae hydrothermal liquefaction wastewater and simultaneously recycling organic element carbon Active CN108517224B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112779044A (en) * 2021-01-05 2021-05-11 江苏大学 Sludge and microalgae supercritical co-rapid hydrothermal liquefaction oil production system and process based on water-phase algae cultivation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1778707A (en) * 2005-10-08 2006-05-31 钱俊 High-concentration ammonia oxidation waste water treatment
CN102071038A (en) * 2009-11-20 2011-05-25 田原宇 Microalgae high-pressure continuous tower-type liquefying process
CN105001971A (en) * 2015-06-26 2015-10-28 新奥科技发展有限公司 Two-step production method for microalgae bio-oil
CN106693837A (en) * 2016-12-02 2017-05-24 河南理工大学 Method for resource regeneration of aquatic plant hydrothermal liquefaction aqueous phase
CN107159679A (en) * 2017-05-17 2017-09-15 浙江大学 A kind of method that fuel oil is produced in Kitchen waste hydrothermal liquefaction

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1778707A (en) * 2005-10-08 2006-05-31 钱俊 High-concentration ammonia oxidation waste water treatment
CN102071038A (en) * 2009-11-20 2011-05-25 田原宇 Microalgae high-pressure continuous tower-type liquefying process
CN105001971A (en) * 2015-06-26 2015-10-28 新奥科技发展有限公司 Two-step production method for microalgae bio-oil
CN106693837A (en) * 2016-12-02 2017-05-24 河南理工大学 Method for resource regeneration of aquatic plant hydrothermal liquefaction aqueous phase
CN107159679A (en) * 2017-05-17 2017-09-15 浙江大学 A kind of method that fuel oil is produced in Kitchen waste hydrothermal liquefaction

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112779044A (en) * 2021-01-05 2021-05-11 江苏大学 Sludge and microalgae supercritical co-rapid hydrothermal liquefaction oil production system and process based on water-phase algae cultivation

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