CN114045311A - Method for preparing biogas from citrus pulp - Google Patents

Method for preparing biogas from citrus pulp Download PDF

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Publication number
CN114045311A
CN114045311A CN202111242940.8A CN202111242940A CN114045311A CN 114045311 A CN114045311 A CN 114045311A CN 202111242940 A CN202111242940 A CN 202111242940A CN 114045311 A CN114045311 A CN 114045311A
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citrus pulp
biogas
citrus
acid
preparing
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CN202111242940.8A
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陈新德
熊莲
姚时苗
王璨
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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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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P5/00Preparation of hydrocarbons or halogenated hydrocarbons
    • C12P5/02Preparation of hydrocarbons or halogenated hydrocarbons acyclic
    • C12P5/023Methane
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05FORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F5/00Fertilisers from distillery wastes, molasses, vinasses, sugar plant or similar wastes or residues, e.g. from waste originating from industrial processing of raw material of agricultural origin or derived products thereof
    • C05F5/002Solid waste from mechanical processing of material, e.g. seed coats, olive pits, almond shells, fruit residue, rice hulls
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/20Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/30Fuel from waste, e.g. synthetic alcohol or diesel

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biotechnology (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Microbiology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Mechanical Engineering (AREA)
  • Botany (AREA)
  • Environmental & Geological Engineering (AREA)
  • Fertilizers (AREA)

Abstract

The invention discloses a method for preparing biogas from citrus pulp, which is characterized in that the citrus pulp is subjected to hydrolytic fermentation to prepare the biogas, the treatment time is short, the purpose of treating a large amount of citrus pulp in a short time can be met, distributed energy can be obtained, a high-efficiency anaerobic reactor can treat high-concentration organic sewage when the citrus pulp is not treated and is idle, the method has important practical and practical significance, and the problem that the citrus pulp produced in a large amount in a short time needs to be put into large-scale fermentation equipment, and the citrus peel industry chain cannot be driven to utilize the pulp in economic benefit is solved.

Description

Method for preparing biogas from citrus pulp
The technical field is as follows:
the invention relates to the technical field of environment-friendly and renewable distributed energy, in particular to a method for preparing biogas from citrus pulp.
Background art:
the citrus pulp related by the invention is from the remainder of the citrus reticulata branch planted in the Jiangmen area and used for producing dried orange peel after removing the peel. The dried orange peel is a geographical marking product in the new meeting and the four-meeting area of the river, has high medicinal value, but a large amount of citrus pulp is left after the peel is extracted, and about 4-6 ten thousand tons per year. The citrus pulp is sour and astringent in taste and is rarely eaten, and is discarded as waste for a long time, so that serious environmental pollution is caused. Some researchers have explored high-value utilization approaches for this purpose. For example, patent CN 108260699A, CN 108185336 a discloses a method for post-treatment of waste citrus pulp, which comprises separating citrus pulp from citrus juice, soaking honey to prepare citrus jam and citrus dried meat, and oven-drying citrus fruit to obtain medicinal materials. Patent CN 104286735A prepares citrus pulp into jam. The patent CN 106387736A adopts an advanced cooling vacuum dehydration technology, retains the original nutritive value of fresh vegetables and fruits, and combines the characteristics of recovery in water with health tea, thereby preparing the tea cake. CN 110272784B discloses a bathroom cleaner containing chazu orange juice and a preparation method thereof; the patent CN 110655430A discloses a method for preparing an organic fertilizer by using citrus pulp residues, wherein 0.2-1% of a leaven, 0.2-1% of a fermentation starter, 10-89% of citrus pulp residues of dried orange peel and the balance of water are fermented to produce a biological organic fertilizer which can be used for plants and has the function of a foliar fertilizer. The invention discloses a liquid feed for fattening pigs, which is prepared by fermenting citrus reticulata pulp and bean dregs through a compound bacterium-enzyme preparation liquid. Patent CN 103131587B discloses a slag-free emission production method of bitter-free citrus pulp fruit wine. The method comprises the steps of selecting citrus fruits, peeling, washing, crushing, liquefying, removing seeds and debitterizing to obtain citrus pulp juice, and preparing the citrus pulp fruit wine without bitter taste through the working procedures of fermentation and the like; the pericarp is used for preparing pericarpium Citri Tangerinae and green and red shreds; drying the seeds in the sun for oil pressing; the wine lees are used for preparing crude yeast, and the production without residue discharge is realized. Patent CN 106138353A discloses a production method of Xinhui citrus antialcoholic enzyme, which comprises the following steps: taking fresh Xinhui citrus reticulata pulp, squeezing juice, filling into a fermentation tank, respectively inoculating Xinhui citrus reticulata enzyme flora, adding kudzu root, plum and sow thistle, and fermenting twice to prepare the anti-alcoholic beverage with the effects of clearing heat and removing toxicity, and expelling toxin and inducing diuresis. CN 112852575A relates to a preparation method of citrus reticulata blanco, which comprises the following steps:
(1) pretreatment before fermentation; (2) pre-fermentation; (3) fermenting after separating the residue and the juice; (4) steaming brandy by a liquid method, adding processed Xinhui mandarin orange leaves into the white spirit, and performing purification for 30 days; (5) the post-treatment comprises filtering, sterilizing, bottling, filtering with one of diatomite, thin plate and microporous membrane, and bottling. The patent CN 111137873A takes Xinhui citrus pulp as a raw material, and a novel carbon material is prepared by a step-by-step carbonization method under the auxiliary action of ammonium bicarbonate. Patent CN 106262685 a discloses a method for making soy sauce with citrus pulp. Patent CN 108947648B discloses a fermentation fertilizer using edible fungus dregs and tangerine peel meat dregs as raw materials. However, in the preparation of foods such as ferment, preserved fruit and fruit wine, the sanitary requirement is strict in the process of taking the citrus peel, the requirement on the freshness of the citrus peel is high, the market accommodation scale of products such as ferment and fruit wine is limited, the fermentation time for preparing fertilizer is long, the citrus peel produced in a large amount in a short time needs to be put into large-scale fermentation equipment, and the citrus peel industry chain cannot be driven to utilize the citrus peel in economic benefit.
The invention content is as follows:
the invention aims to provide a method for preparing biogas from citrus pulp, wherein the citrus pulp is subjected to hydrolytic fermentation to prepare the biogas, the treatment time is short, the purpose of treating a large amount of citrus pulp in a short time can be met, distributed energy can be obtained, and a high-efficiency anaerobic reactor can treat high-concentration organic sewage when the citrus pulp is not treated and is idle, so that the method has important practical and practical significance, and the problems that a large amount of citrus pulp produced in a short time needs to be put into large-scale fermentation equipment, and a citrus peel industry chain cannot be driven to utilize the pulp in economic benefit are solved.
The invention is realized by the following technical scheme:
a method for preparing biogas from citrus pulp comprises the following steps: the citrus pulp is conveyed into a reaction kettle by a spiral feeder, heated to 198-ion 202 ℃ under the stirring condition and reacted for a period of time, then solid-liquid separation is carried out by a filter press or a horizontal spiral centrifuge, alkali is added into the liquid for neutralization until the pH value is 6.5-8.5, then the liquid is pumped into an efficient anaerobic reactor for producing biogas, effluent is discharged after aerobic biological treatment and physicochemical treatment, and a small amount of residues are sold as organic fertilizer raw materials or directly buried.
The citrus pulp can be hydrolyzed at the higher temperature of 198-202 ℃ because the citrus pulp contains acid, and preferably, no more than 3.0 percent of acid or enzyme is also added into the reaction kettle; the acid is more than one of sulfuric acid, hydrochloric acid, acetic acid, formic acid and oxalic acid; the enzyme is a mixture of pectinase, hemicellulase, xylanase and cellulase, and the total enzyme activity is more than or equal to 10000U/g; reacting for 0.5-3h at 80-200 ℃ under the condition of acid catalysis; reacting for 24-72h at 25-37 ℃ under the condition of adding enzyme.
The citrus pulp is obtained from the remainder of citrus reticulata branch planted in the Jiangmen area and used for producing dried orange peel after removing peel.
Preferably, the stirring speed is 50-150 rpm.
Preferably, the water content of the solid part after solid-liquid separation is 25-45%.
The alkali for neutralization is CaO, Ca (OH)2、NaOH、Na2CO3、NaHCO3More than one of them.
The anaerobic reactor is selected from one of an up-flow anaerobic sludge bed reactor (UASB), an anaerobic expanded granular sludge bed reactor (EGSB), an internal circulation anaerobic reactor (IC) and a double-circulation high-efficiency anaerobic reactor, and the organic load is 2-25 kg/Nm3The residence time is 6-12 h.
The invention has the following beneficial effects: can effectively utilize mandarin orange meat, turn into the energy with it, and handle and take time for short, the handling capacity is big, and the marsh gas of production is splendid distributed energy, and produces the anaerobic reactor of marsh gas and still can be used to handle high concentration organic waste water in non mandarin orange meat output season, and anaerobic reactor still can be used to sewage treatment in mandarin orange meat slack season, and equipment input output is higher, has important realistic meaning.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1
Conveying the mandarin orange meat to a reaction kettle by a screw feeder, heating to 200 deg.C, stirring at 50rpm for 3 hr, performing solid-liquid separation by a filter press after flash evaporation and cooling, neutralizing the liquid with NaOH to pH6.5, pumping into UASB to produce biogas with an operation load of 2kg/Nm3D, the retention time is 6h, and the biogas yield is 90Nm3One ton of citrus pulp. Effluent is discharged after aerobic biological treatment and physicochemical treatmentAnd a small amount of residues are sold as organic fertilizer raw materials or directly buried for treatment.
Example 2
Conveying the mandarin orange meat to a reaction kettle by a screw feeder, adding 3 wt% acetic acid, heating to 130 deg.C, stirring at 100rpm for 0.5 hr, cooling by a heat exchanger, performing solid-liquid separation by a filter press, adding Na into the liquid2CO3Neutralizing to pH8.5, pumping EGSB to produce marsh gas with operation load of 15kg/Nm3D, the retention time is 12h, and the biogas yield is 94Nm3One ton of citrus pulp. The effluent is discharged after reaching standards through aerobic biological treatment and physicochemical treatment, and a small amount of residues are sold as organic fertilizer raw materials or directly buried.
Example 3
Conveying the mandarin orange meat to a reaction kettle by a spiral feeder, adding 1.5 wt% sulfuric acid, heating to 80 deg.C, stirring at 150rpm for reaction for 3h, performing solid-liquid separation by a filter press after flash evaporation and cooling, adding CaO into the liquid for neutralization to pH6.5, pumping into an IC reactor to produce biogas with an operation load of 25kg/Nm3D, the retention time is 8h, and the biogas yield is 65Nm3One ton of citrus pulp. The effluent is discharged after reaching standards through aerobic biological treatment and physicochemical treatment, and a small amount of residues are sold as organic fertilizer raw materials or directly buried.
Example 4
Conveying mandarin orange meat to a reaction kettle by a screw feeder, adding 0.5 wt% hydrochloric acid, heating to 170 deg.C, stirring at 50rpm for 1 hr, performing solid-liquid separation by a filter press after flash evaporation and cooling, neutralizing the liquid with NaOH to pH7.0, pumping into UASB to produce biogas with a running load of 5kg/Nm3D, the retention time is 12h, and the biogas yield is 80Nm3One ton of citrus pulp. The effluent is discharged after reaching the standard through aerobic biological treatment and physicochemical treatment, and a small amount of residues are sold as organic fertilizer raw materials or directly buried.
Example 5
Conveying the mandarin orange meat to a reaction kettle by a screw feeder, adding 2 wt% of oxalic acid, heating to 145 ℃, stirring at 80rpm for reaction for 2h, performing solid-liquid separation by a filter press after flash evaporation and temperature reduction, and adding Ca (OH) into the liquid2Neutralizing to pH7.5, pumping into a dual-circulation anaerobic reactor to produce biogas with an operation load of 18kg/Nm3D, the retention time is 10h, and the biogas yield is 90Nm3One ton of citrus pulp. The effluent is discharged after reaching standards through aerobic biological treatment and physicochemical treatment, and a small amount of residues are sold as organic fertilizer raw materials or directly buried.
Example 6
Conveying the mandarin orange meat into a reaction kettle by using a spiral feeder, adding 1.2 wt% of formic acid, heating to 170 ℃, stirring at 70rpm for reaction for 2.5h, performing solid-liquid separation by using a filter press after flash evaporation and temperature reduction, adding NaOH into the liquid for neutralization to pH7.5, pumping the liquid into an IC reactor to produce biogas, wherein the operation load is 20kg/Nm3D, the retention time is 8h, and the biogas yield is 97Nm3One ton of citrus pulp. The effluent is discharged after reaching standards through aerobic biological treatment and physicochemical treatment, and a small amount of residues are sold as organic fertilizer raw materials or directly buried.
Example 7
Conveying the mandarin orange meat to a reaction kettle by a screw feeder, adding 0.8 wt% of formic acid and 0.5 wt% of sulfuric acid, heating to 125 deg.C, stirring at 120rpm for reaction for 0.8h, performing solid-liquid separation by a filter press after flash evaporation and temperature reduction, adding Ca (OH) into the liquid2Neutralized to pH4.5 and then NaHCO was added3When the pH value is 8.0, pumping UASB to produce biogas, and the operation load is 13kg/Nm3D, the retention time is 10h, and the biogas yield is 80Nm3One ton of citrus pulp. Effluent is discharged after reaching standards through aerobic biological treatment and physicochemical treatment, and a small amount of residue has the water content of 45 percent and is sold as an organic fertilizer raw material or directly buried.
Example 8
Conveying the citrus pulp into a reaction kettle by using a spiral feeder, heating to 37 ℃, adding a mixture of pectinase, hemicellulase, xylanase and cellulase (the mass ratio is 1:1:1:1), stirring at 150rpm for reaction for 72 hours, adjusting the pH of liquid to 7.5 after solid-liquid separation, pumping into an IC reactor to produce biogas, and controlling the operation load to be 25kg/Nm3D, the retention time is 6h, and the biogas yield is 81Nm3One ton of citrus pulp. The effluent is discharged after reaching the standard through aerobic biological treatment and physicochemical treatment, and the residue with the water content of 25 percent is sold as an organic fertilizer raw material or directly buried.
Example 9
Conveying the citrus pulp into a reaction kettle by using a spiral feeder, heating to 25 ℃, adding a mixture of pectinase, hemicellulase, xylanase and cellulase (the mass ratio is 0.5:0.5:1:1), regulating the total enzyme activity to 50000U/g, stirring at 50rpm for reaction for 24 hours, after solid-liquid separation, regulating the pH of liquid to 6.5, pumping the liquid into a UASB reactor to produce biogas, and controlling the operation load to 10kg/Nm3D, the retention time is 10h, and the biogas yield is 67Nm3One ton of citrus pulp. The effluent is discharged after reaching the standard through aerobic biological treatment and physicochemical treatment, and the residue with 35 percent of water content is sold as an organic fertilizer raw material or directly buried.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.

Claims (7)

1. The method for preparing the biogas from the citrus pulp is characterized by comprising the following steps: the citrus pulp is conveyed into a reaction kettle by a spiral feeder, heated to 198-ion 202 ℃ under the stirring condition and reacted for a period of time, then solid-liquid separation is carried out by a filter press or a horizontal spiral centrifuge, alkali is added into the liquid for neutralization until the pH value is 6.5-8.5, then the liquid is pumped into an efficient anaerobic reactor for producing biogas, effluent is discharged after aerobic biological treatment and physicochemical treatment, and a small amount of residues are sold as organic fertilizer raw materials or directly buried.
2. The method for preparing biogas from citrus pulp according to claim 1, wherein not more than 3.0 wt% of acid or enzyme is further added to the reaction kettle; the acid is more than one of sulfuric acid, hydrochloric acid, acetic acid, formic acid and oxalic acid; the enzyme is a mixture of pectinase, hemicellulase, xylanase and cellulase, and the total enzyme activity is more than or equal to 10000U/g; reacting for 0.5-3h at 80-200 ℃ under the condition of acid catalysis; reacting for 24-72h at 25-37 ℃ under the condition of adding enzyme.
3. The method for preparing biogas from citrus pulp according to claim 1 or 2, wherein the citrus pulp is obtained from the remainder of citrus reticulata branch for producing dried orange peel, which is planted in the Jiangmen area, after peeling.
4. The method for preparing biogas from citrus pulp according to claim 1 or 2, characterized in that the stirring speed is 50-150 rpm.
5. The method for preparing biogas from citrus pulp according to claim 1 or 2, wherein the moisture content of the solid part after the solid-liquid separation is 25% to 45%.
6. Method for producing biogas from citrus pulp according to claim 1 or 2, characterized in that the alkali used for neutralization is CaO, Ca (OH)2、NaOH、Na2CO3、NaHCO3More than one of them.
7. The method for preparing biogas from citrus pulp according to claim 1 or 2, wherein the anaerobic reactor is selected from one of an upflow anaerobic sludge bed reactor, an anaerobic expanded granular sludge bed reactor, an internal circulation anaerobic reactor and a double circulation high efficiency anaerobic reactor, and the organic load is 2-25 kg/Nm3The residence time is 6-12 h.
CN202111242940.8A 2021-10-25 2021-10-25 Method for preparing biogas from citrus pulp Pending CN114045311A (en)

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