CN104843850B - Method by industrial organic sewage conversion processing - Google Patents
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- CN104843850B CN104843850B CN201510235327.1A CN201510235327A CN104843850B CN 104843850 B CN104843850 B CN 104843850B CN 201510235327 A CN201510235327 A CN 201510235327A CN 104843850 B CN104843850 B CN 104843850B
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- 239000010865 sewage Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 55
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- 238000012545 processing Methods 0.000 title claims abstract description 9
- 239000000446 fuel Substances 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Liquid Carbonaceous Fuels (AREA)
Abstract
Disclosing a kind of method by industrial organic sewage conversion processing, it comprises the steps: that industrial organic sewage is collected in sewage conservation tank by (1)；(2) deodorizer and/or insecticide biologic formulation are put in formula conservation tank；(3) sewage step (1) collected puts into stirring in agitator with the biologic formulation of step (2) by the weight ratio of 1:9 9:1；(4) putting into after stirring in converting apparatus and convert, conversion temperature is 20 35 DEG C；(5) converted product is further processed, it is thus achieved that alcohol-based fuel.The alcohol-based fuel obtained by the method has preferable fuel performance index such as Cetane number and oxidation stability.
Description
Technical field
The invention belongs to field of environmental technology, relate to resourcable transformation and the utilization of organic sewage, particularly to organic wastewater treatment, more specifically it relates to a kind of method by difficult-degradation organic sewage conversion processing.
Background technology
Industrial organic sewage refers in the animal farm of farming and animal husbandry, hennery, slaughterhouse, the sewage containing organic principles such as sulfur, oxygen, nitrogen, ammonia of the various stenches that various chemical industry, Electroplate Factory, printing and dyeing mill and the municipal refuse disposal area of industry, hospital, public lavatory etc. generate, it is also called VOC, there is concentration high (COD, BOD), the feature that difficult, hazardness is big.
Along with the development and application field of microbial fermentation engineering technology the most constantly extends, utilize sewage manufacture to process the developing history process of the energy, the process of sewage mainly used following three kinds of processing methods:
First method is to utilize organic sewage to produce biogas.More than 200 year history has been had since within 1776, Italian scientist C.A.volta invention organic sewage can produce biogas, nowadays biogas scientist in countries in the world adds Fructus Citri tangerinae bar, the mixing of organic rot organic sewage, in the case of suitable temperature, humidity, the fermentation of acid-base value microbiological anaerobic, make biogas, novel process energy substitution oil as one, natural gas has been widely used.Ending for the end of the year 2003 according to statistics, China utilizes organic wastewater to build together 600 biogas engineerings, anaerobic pond volume 150 ten thousand stere, and year processes organic wastewater 1.5 billion cubic meter；Within 2006, national rural area utilizes organic sewage construction of marsh gas tank more than 18,000,000.Although organic sewage fermentation producing methane technology is ripe, but about 6 years investment repayment phases, economic value added is low.
Second method is to utilize organic sewage to produce hydrogen.According on May 11st, 2008 " science Times ", Harbin Institute of Technology of China was in 2005, undertake national " 863 " plan, utilize microbe fermentation method, organic sewage can be produced hydrogen and found the factory, day hydrogen producing 1200 cubic metres, become Article 1 dark microbial fermentation for bio-hydrogen production production line in the world, but manufacturing cost is high, it is difficult to industrialized development.The U.S., Britain scientific research personnel utilize " electric shocking method " electric shock organic wastewater hydrogen producing fuel, can provide power to vehicle by replacing gasoline, and this technology is because production cost is high, be difficult to promotion and application.
The third method is to utilize sewage to produce hybrid fuel.In this place in reason method, sewage is processed, be converted to the mud containing relatively high organic content, then clear up processing procedure by micro-oxygen and be hydrolyzed acidifying, it is thus achieved that fatty acid.
CN102827661A discloses a kind of sludge from wastewater treatment plant turning sludge into fuel and processes process, it is characterized in that: the method comprises the steps: that (1) carries out chemical conditioning to mud, adding high polymer coagulant in mud by a certain percentage and surfactant stirs, every kilogram of mud adds high polymer coagulant 3.5 ~ 4.0g, surfactant 4.0 ~ 4.5g；(2) mud carrying out physics conditioning, add dispersant by a certain percentage and stir in mud, every kilogram of mud adds dispersant 110 ~ 130g；(3) mud being carried out microwave radiation conditioning, be sent in microwave oven carry out microwave radiation, microwave irradiation power is 600w, and radiated time is 250 ~ 300s；(4) mud being carried out mechanism filter-pressing dehydration, the mud after being nursed one's health by microwave radiation is sent in pressure filter, keeps certain pressure, filter pressing certain time so that it is reach the limit of filter-press dehydration；Filter pressing pressure is 0.8MPa, and time of filter pressing is 30 ~ 45min, and after filter pressing, moisture content of the cake is less than 50%, and quality is down to original about 40%；(5) again the mud after dehydration is carried out pelletize；(6) mud is carried out microwave drying treatment, the mud of pelletize send into microwave oven be dried, molding；Microwave power 600w, every kilogram of drying sludge time is 30 ~ 45min, obtains the sludge fuel that moisture content is about 5 ~ 10% after drying.
CN102373103A discloses a kind of method utilizing sludge from wastewater treatment plant production to process fuel, it comprises the following steps: (one) pretreatment of raw material, in the mud that municipal sewage plant produces, addition straw is or/and waste residue of Chinese herbs, is stirred by mixed material with horizontal mixer；(2) drying and moulding sterilization processing, is transported to drum dryer step (one) gained mixture, material is dried process, simultaneously works as bactericidal action；After drum dryer processes, the moisture content of material is reduced to 40～50%, and material is granulated simultaneously, and particle diameter is 2～10mm；(3) redrying sterilization, from drum dryer granular material out, delivers to solar energy and artificial underground heat booth makees further mummification, sterilization processing, and through 24～48h dried, material water ratio is down to 8～15%.
CN103910473A discloses a kind of production technology that organic sewage is converted to liquid fuel, it is characterized in that, described organic sewage is municipal refuse penetrating fluid and/or kitchen sewage, its production technology being converted to liquid fuel comprises the following steps: 101) pretreating sewage: organic sewage introduces sewage collecting pool and carries out sewage collecting, more described organic sewage introduced sewage preparing pool, and add biological preparation above-mentioned sewage is purified and deodorization, biological preparation includes insecticide and deodorizer；102) under room temperature, normal pressure, anaerobic condition, in the organic sewage of pretreatment, fermentation and acid is carried out by multiple-microorganism mushroom；103) by multi-stage biochemical reaction unit, under the effect of multiple-microorganism mushroom, described organic sewage is converted into composite fluid fuel.
CN102311813A discloses a kind of method of extracting liquid fuel by waste sewage, is first collected by trade effluent and is positioned in water cellar, then oleagenous plant is put into sewage in cellar for storing things, carries out soaking fermentation；After sewage is fermented, then cellar for storing things will be extracted out and carry out precipitation and filter and separate the liquid that ferment, the Organic substance liquid stock solution obtained, interpolation help 30～50% combustion agent after be liquid fuel.Wherein, in the industry collected and sanitary sewage, throw in the tree branches and leaves of oleagenous plant, ferment under normal temperature and pressure state, then the liquid fermented in cellar for storing things extraction is carried out precipitation filtration and separate, the Organic substance liquid stock solution obtained, then become liquid fuel after adding methanol or ethanol combustion adjuvant.
nullCN102732334A discloses a kind of oleagenous plant and method that grease-contained discarded sewage is raw material production biological liquid fuel，It is characterized by orderly comprising following steps: A、By grease-contained discarded sewage remove impurity，Add in esterification device，It is simultaneously introduced the fresh Eucalyptus branch and leaf being ground into 3-5 centimetre，It is simultaneously introduced methanol and iron sulfate，Iron sulfate is as catalyst，Grease-contained discarded sewage quality is 100 parts，Fresh Eucalyptus branch and leaf quality is 50 parts，Iron sulfate quality is 2-4 part，Methanol quality is 10-30 part，Heating bath is warming up to about 100 DEG C，Then the methanol vaporized in vapourizing unit is passed through in esterification device，Methanol and raw material carry out intense reaction at relatively high temperatures，Response time is 2-4 hour，After reaction terminates，Iron sulfate and fresh Eucalyptus branch and leaf are stood or centrifugal separatory is separated；B, add 10-20 mass KOH to esterification device, heating bath temperature is risen to 60-90 DEG C and carries out ester exchange reaction 1-2 hour；C, being separated by mixed liquor, separate glycerin layer, first upper strata methyl ester carries out air-distillation, reclaim the methanol of excess, then wash with appropriate dilute acid soln, be washed with water to water layer be neutrality, finally carrying out vacuum distilling and obtain biodiesel, lower floor is by-product glycerin.
CN101830621A discloses a kind of sludge drying, the system of turning sludge into fuel process and corresponding technique thereof, including one-level blade dryer and two grades of blade dryers, sludge pump is connected with the charging aperture of one-level blade dryer by pipeline, the discharging opening of one-level blade dryer connects the feeding mouth of two grades of blade dryers, and there is a sub-material plate in two grades of blade dryer exits is connected with back-mixing device；Its technological process is: mud is delivered to one-level blade dryer by a., and the rotating speed of the double plate blade dryer of one-level is 2.5～3.5 revs/min, and steam uses 0.45～0.55MPa, and temperature is 160～180 DEG C, and slightly band negative pressure-500～-800Pa；B. deliver to mud again two grades of blade dryers continue be dried, the rotating speed of two grades of double plate blade dryers controls at 30～38 hertz, and i.e. 8～10 revs/min, steam uses 0.55～0.65MPa, temperature is 160～180 DEG C, whole anhydration system slightly band negative pressure-600～-800Pa；C. the 30-50% in two grades of dried dry mud of blade dryer automatically returned to one-level blade dryer by back-mixing device and carry out mummification operation in the lump with the mud being newly added.
CN101914404A discloses a kind of method of preparing solid fuel from sludge of sewage treatment plant, it is characterized in that: (1) sludge pretreatment: take the sewage treatment plant's wet mud after mechanical dehydration, water is added than 0.5～1: 1 by the volume mass of water with wet mud, it is that the 93%～98% technical grade sulphuric acid volume mass with wet mud is than 5～20: 1000 addition sulphuric acid by mass concentration, it is that 27.5%～35% industrial grade hydrogen peroxide volume mass with wet mud is than 10～50: 1000 addition hydrogen peroxide by mass concentration, the sludge slurry adding sulphuric acid and hydrogen peroxide is stirred and is heated to 45 DEG C～95 DEG C, mud is carried out pretreatment, pretreatment time 5min～90min；After pretreatment filtering sludge slurry and wash with water, washings consumption is 1～4: 1 with the volume mass ratio of wet mud, obtains mud cake and filtrate after filtration washing；(2) mud cake prepares solid fuel: regulate the pH value of mud cake to 6.5～7.5 with pulverized limestone, the mud cake that have adjusted pH value is loaded in dry distilling tank and carries out dry distilling, needed for dry distilling, thermal source is with the solar energy of convex lens focus sunlight gained, focusing sunlight is directly radiated equipped with on the dry distilling tank of mud cake；When the moisture of the retorted product in dry distilling tank is less than 1.0%, dry distilling completes, and takes out retorted product, obtains solid fuel.
CN1743415A discloses device and the application process thereof of a kind of preparing liquid fuel by catalytic pyrolysis of sewage and sludge, and its device is mainly made up of nitrogen cylinder (source), heating furnace, temperature controller, condenser, liquid-phase collection bottle, surge flask, absorption bottle, airbag, raw material pyrolysis reactor etc..The method of preparing liquid fuel is that the pyrolysis reactor that will be equipped with a certain amount of oily sludge and catalyst is put in heating furnace, open cooling water, switch on power, set temperature program to heat, heating rate is 5～10 DEG C/min, temperature-rise period stops 30～40 minutes, is heated to 500～600 DEG C.In the cracked oil that oily sludge prepares after pyrolysis, gasoline content reaches as high as 20%, and diesel oil about 50%, remaining is heavy oil；In the fuel gas of pyrolysis gained, the content of C6+ component may be up to 40%.Pyrolyzing sludge can get low-carbon (LC) hydrocarbon gas, liquid-fuel oil, the burnt three class materials of solid, and wherein solid Jiao can activate further and be processed as material with carbon element, thus the complete resource realizing oil-polluted water mud processes.
CN102491608A discloses the production method of a kind of sewage sludge biomass environment-friendly fuel, comprises the steps: 1) sludge pretreatment: mud is delivered to pretreatment pool, and adds deodorizer, antibacterial, stir；2) sludge modification: pretreated mud is delivered to reaction tank, and adds modifying agent, sulphur-fixing agent, heavy metal stabilizer, after homogeneous reaction, adds size-reduced biomass；3) deeply dehydrating sludge: modified mud carries out deep dehydration；4) drying sludge: the mud cake after deep dehydration is dried process after crushing.
EP1368463A2 discloses a kind of method of solid waste processed containing adverse chemical product, described method includes adding multiple yeast cells in solid waste, make yeast cells degraded adverse chemical product, wherein said multiple yeast cells includes at least one of the following: (a) by by yeast cells in the range of frequency is 52 to 98MHz, field intensity be the yeast cells that prepared by cultivation in of 8 to 300mV/cm or one group of electromagnetic field, its can degrade toluene, ethylbenzene or trichlorophenol, 2,4,6,-T；(b) by by yeast cells in the range of frequency is 30 to 50MHz or 70 to 98MHz, field intensity be to cultivate the yeast cells prepared, its xylene compounds of can degrading in one of 8 to 250mV/cm or one group of electromagnetic field；(c) by by yeast cells in the range of frequency is 70 to 98MHz or 133 to 151MHz, field intensity be to cultivate the yeast cells prepared, its benzaldehyde of can degrading in one of 8 to 250mV/cm or one group of electromagnetic field；(d) by by yeast cells in the range of frequency is 70 to 98MHz or 145 to 162MHz, field intensity be to cultivate the yeast cells prepared, its propionic aldehyde of can degrading in one of 8 to 250mV/cm or one group of electromagnetic field；(e) by by yeast cells in the range of frequency is 70 to 100MHz, field intensity be to cultivate the yeast cells prepared, its enanthaldehyde of can degrading in one of 8 to 250mV/cm or one group of electromagnetic field；(f) by by yeast cells in the range of frequency is 70 to 98MHz or 163 to 183MHz, field intensity be to cultivate the yeast cells prepared, its dichloro-benzenes of can degrading in one of 8 to 250mV/cm or one group of electromagnetic field.
US5871618A discloses a kind of apparatus and method from waste oil disposal fuel oil.This device includes thermal cracking unit, becomes lighter lower boiling material for the high boiling hydrocarbon material of cracking so that from stickum separation hydrocarbon steam product；Condenser/heat exchanger, becomes liquid hydrocarbon for condensation of hydrocarbons steam product；Fuel stabilization equipment, for chemical treatment condensate, in order to obtain oil product and solid sediment；And accurate process equipment, it is used for removing solid pollutant by physical method and forms high-quality fuel oil.
" municipal sludge prepares molding derivatived fuel technology summary ", Li Hui etc., new forms of energy are in progress, the 1st phase of volume 2, in February, 2014 illustrates existing mud forming technique, including sludge drying molding, semi-oriented molding and wet type forming technique etc., emphasis illustrates its respective pluses and minuses, it is indicated that sludge drying molding is the major way of following mud molding.
In the prior art including above-mentioned document, it is all that the mixture of fatty acid and the alcohol obtained by acid process is collected, transfers fatty acid methyl ester to directly as alcohol-based fuel rather than by the fatty acid of generation.But, there is the features such as Cetane number is low, oxidation stability is poor in such fuel element.Therefore, fatty acid converted in-situ is fatty acid methyl ester by the present inventor, thus drastically increases fuel value and the oxidation stability of alcohol-based fuel.
Further, traditional esterification technique is acid technique or alkali technique, but when using conventional acid base catalysator, transformation efficiency is low, and needs to use larger amount of acid base catalysator, causes subsequent product purification and recycling difficulty；When using enzyme esterification process, catalyst is harsh to the quality requirements of reactant, it is difficult to is applied in the esterification of fatty acid obtained as raw material using sewage, to this end, the present invention is through great many of experiments, have developed a kind of catalyst for esterification reaction being suitable for the inventive method.
Summary of the invention
For solving the above-mentioned problems in the prior art, the present inventor is through further investigation and lot of experiments, it is provided that solution.
In one aspect of the invention, it is provided that a kind of method by industrial organic sewage conversion processing, it comprises the steps:
(1) organic sewage is collected in sewage conservation tank；
(2) deodorizer and/or insecticide biologic formulation are put in formula conservation tank；
(3) sewage step (1) collected puts into stirring in agitator with the biologic formulation of step (2) by the weight ratio of 1:9-9:1；
(4) putting into after stirring in converting apparatus and convert, conversion temperature is 20-35 DEG C；With
(5) converted product is further processed, it is thus achieved that alcohol-based fuel.
Described alcohol-based fuel is the mixture comprising fatty acid methyl ester and alcohol, it is also possible to be referred to as bio-fuel.Owing to comprising a certain amount of alcohol in this fuel, it is also referred to as alcohol-based fuel the most in the present invention.
In a preferred embodiment, in step (1), it is also possible to include being enriched with the organic component in organic sewage.
In step (2), the biologic formulation of described deodorizer and/or insecticide can be prepared with water.Its concentration can determine according to actual effect.
Preferably, described deodorizer is blended by Fructus Amomi Rotundus, Fructus Amomi, Semen Myristicae, Cortex Cinnamomi, Radix Cinnamomi porrecti, Fructus Foeniculi, the Radix Aucklandiae, the Radix Angelicae Dahuricae, Rhizoma Kaempferiae, Rhizoma Alpiniae Officinarum, and Fructus Amomi Rotundus, Fructus Amomi, Semen Myristicae, Cortex Cinnamomi, Radix Cinnamomi porrecti, Fructus Foeniculi, the Radix Aucklandiae, the Radix Angelicae Dahuricae, Rhizoma Kaempferiae, the weight ratio of Rhizoma Alpiniae Officinarum are (5-10)
: (1-3) : (1-2) : (1-2) : (1-3) : (2-3) : (1-3) : (1-5) : (1-5) : (1-2).Mix with deodorization bacterium.
Preferably, described insecticide by selected from Azadirachta Indica A., Melia azedarach L., Celastrus angulatus, raw Folium pterocaryae stenopterae, bitter Folium Nelumbinis, eucalyptus leaves, raw Nicotiana tabacum L., Pyrethrum, Ramulus et folium taxi cuspidatae, Herba Portulacae, open in fiber crops, the Radix Pulsatillae, Herba Chelidonii, Radix Agrimoniae, Radix Angelicae Pubescentis, the Rhizoma Pinelliae, Herba speranskiae tuberculatae, Herba Menthae, Northeastern Radix Gentianae, ovum leaf Radix Paeoniae, Herba Xanthii, the Fructus Kochiae at least three kinds be blended with effective dose, mix with bacterium for killing insect.Described effective dose refers to play the amount of required insecticidal effect.
Preferably, described converting apparatus includes retort, all adds biological mushroom and realize converting in each retort.
It is further preferred that described retort there was added deodorization bacterium, division bacterium, acid-producing bacteria, zymocyte, suction carbon bacterium, produce alcohol bacterium, the mixture of one or more gone in heavy metal bacterium.Described mushroom can be the conventional mushroom in this area, can be purchased or obtained by conventional culture methods.The addition of described biological mushroom can be added by inocalation method.
Additionally or preferably, described retort adds nitrogen-fixing bacteria acid-producing bacteria.
Further preferably adding acid-producing bacteria, zymocyte and product alcohol bacterium dilution bacterium, corruption bacterium and the mixture of adhered bacteria, this mixture is acid-producing bacteria, zymocyte and product alcohol bacterium dilution bacterium, degenerates bacterium and adhered bacteria three with (5-10): (1-2): the mixture of (3-8) bacterium number ratio.
Preferably, in step (5), add methanol, carry out esterification in the presence of a catalyst, thus convert fatty acids step (4) produced is fatty acid methyl ester, isolates fatty acid methyl ester and alcohols, obtains alcohol-based fuel.Methanol is preferably (1.1-1.5) with the mol ratio of fatty acid: 1.
It is particularly preferred that described catalyst is solid super acid catalyst, it can be expressed as SO4 2-/SnO2-ZrO2-beta-molecular sieve.Such catalyst the most not yet has report.In this catalyst, Sn element can be 8:1-15:1, preferably 10:1 with the mol ratio of Zr element；SnO2And ZrO2The weight ratio of gross weight and beta-molecular sieve be (1-10): (50-100).Count based on this catalyst cumulative volume (L), sulfuric acid concentration i.e. SO in catalyst4 2-Concentration be preferably 4.0-6.0mol/L, more preferably 5.0mol/L.
Preferably, described beta-molecular sieve is Hydrogen beta-molecular sieve.It is highly preferred that described beta-molecular sieve is the beta-molecular sieve being stripped of part framework aluminum.Further preferably, the skeleton rate removing ratio of described beta-molecular sieve is 50-80%, inventors have surprisingly discovered that, when removing the framework aluminum of this special ratios, the mesoporous pore size making beta-molecular sieve becomes to be more suitable for the reactant of esterification of the present invention and therefrom passes in and out, thus improves reaction conversion ratio and selectivity.
This catalyst can be prepared by the following method: weigh the SnCl of respective amount by above-mentioned mol ratio4∙5H2O、Zr(NO3)4∙4H2O is placed in container, adds deionized water wiring solution-forming, is subsequently adding beta-molecular sieve, is sufficiently stirred for dispersion and dipping；Under agitation being slowly added dropwise ammonia so that it is be co-precipitated, maintaining pH in whipping process is 7.5-8.0, then filters, is at room temperature aged 8-24 hour by precipitate；By precipitate washing, sucking filtration, dried, impregnate under agitation 2-5 hour with certain density sulfuric acid solution, filter and be dried carrying out, finally carry out high-temperature calcination (such as 300-600 DEG C), it is thus achieved that the solid super acid catalyst of the present invention.
When using the high-performance solid super acidic catalyst of the present invention, catalyst is 1:500 to 1:2000, preferably 1:1000 with the weight ratio of reactant methanol.Few more a lot of than the consumption of conventional solid acid catalyst.Such technique effect is also that those skilled in the art institute is unforeseeable.
Detailed description of the invention
Below by specific embodiment and comparative example, the present invention is described in further detail.But the invention is not restricted to described embodiment.
Embodiment
1
By the sewage collecting from slaughterhouse in sewage conservation tank；Deodorizer and/or insecticide biologic formulation (i.e. preparaton) are put in formula conservation tank；Sewage described in step is put into stirring in agitator with biologic formulation by the weight ratio of 9:1；Putting into after stirring in converting apparatus and convert, there was added acid-producing bacteria (deriving from the sludge anaerobic producing strains of Alderich) in this converting apparatus, conversion temperature is 25 DEG C；It is subsequently adding methanol, fatty acid therein is esterified, collect fatty acid methyl ester and other alcohols, it is thus achieved that alcohol-based fuel.In described esterification, first detecting the content of fatty acid, calculate the quantity of methyl alcohol that should add, methanol is 1.2:1 with the mol ratio of fatty acid, and reaction temperature is 65 DEG C, and the response time is 3h, and the catalyst of use is SO4 2-/SnO2-ZrO2-beta-molecular sieve solid super acid catalyst, wherein, Sn element is 10:1, SnO with the mol ratio of Zr element2And ZrO2The weight ratio of gross weight and beta-molecular sieve be 3:50, based on this catalyst cumulative volume meter, sulfuric acid concentration i.e. SO in catalyst4 2-Concentration be 5.0mol/L.Described catalyst is 1:1000 with the weight ratio of methanol.The performance of the alcohol-based fuel that reaction obtains is as follows:
The net heating value of this fuel and Cetane number are higher than the general bio-fuel from vegetable oil.
Comparative example
1
Operate according to method same as in Example 1, be conventional solid acid catalyst Amberlyst 15 resin catalyst with the catalyst that differs only in of embodiment 1.
Be clear that by contrast, net heating value and the Cetane number of the alcohol-based fuel that comparative example 1 prepares are below the alcohol-based fuel that embodiment 1 obtains, additionally oxidation stability is the most much lower, through analyzing, its reason is that esterification conversion ratio is relatively low, thus causes left more fatty acid in prepared alcohol-based fuel.
This written description uses the open present invention of example, including optimal mode, and also enables those skilled in the art manufacture and use the present invention.The present invention can patentable scope be defined by the claims, and can include other example that those skilled in the art expect.If other example this has the structural element of the literal language not differing from claims, or if other example this includes the equivalent structure element without substantial differences of the literal language with claims, other example the most this is intended to be within the scope of claims.Under not resulting in inconsistent degree, by with reference to by herein with reference to all references in place of be incorporated herein.
Claims (1)
1., by a method for industrial organic sewage conversion processing, it comprises the steps:
(1) organic sewage is collected in sewage conservation tank；
(2) deodorizer and/or insecticide biologic formulation are put in formula conservation tank；
(3) sewage step (1) collected puts into stirring in agitator with the biologic formulation of step (2) by the weight ratio of 1:9-9:1；
(4) putting into after stirring in converting apparatus and convert, conversion temperature is 20-35 DEG C；With
(5) converted product is further processed, it is thus achieved that alcohol-based fuel；
Described deodorizer is blended by Fructus Amomi Rotundus, Fructus Amomi, Semen Myristicae, Cortex Cinnamomi, Radix Cinnamomi porrecti, Fructus Foeniculi, the Radix Aucklandiae, the Radix Angelicae Dahuricae, Rhizoma Kaempferiae, Rhizoma Alpiniae Officinarum, and Fructus Amomi Rotundus, Fructus Amomi, Semen Myristicae, Cortex Cinnamomi, Radix Cinnamomi porrecti, Fructus Foeniculi, the Radix Aucklandiae, the Radix Angelicae Dahuricae, Rhizoma Kaempferiae, the weight ratio of Rhizoma Alpiniae Officinarum are (5-10): (1-3): (1-2):
(1-2) : (1-3) : (2-3) : (1-3) : (1-5) : (1-5) : (1-2)；
Described insecticide by selected from Azadirachta Indica A., Melia azedarach L., Celastrus angulatus, raw Folium pterocaryae stenopterae, bitter Folium Nelumbinis, eucalyptus leaves, raw Nicotiana tabacum L., Pyrethrum, Ramulus et folium taxi cuspidatae, Herba Portulacae, open in fiber crops, the Radix Pulsatillae, Herba Chelidonii, Radix Agrimoniae, Radix Angelicae Pubescentis, the Rhizoma Pinelliae, Herba speranskiae tuberculatae, Herba Menthae, Northeastern Radix Gentianae, ovum leaf Radix Paeoniae, Herba Xanthii, the Fructus Kochiae at least three kinds be blended with effective dose, described effective dose refers to play the amount of required insecticidal effect；
In described step (4), described converting apparatus includes retort, all adds biological mushroom and realize converting in each retort；
Described retort there was added deodorization bacterium, divide bacterium, remove heavy metal bacterium, acid-producing bacteria, zymocyte, suction carbon bacterium, the mixture of one or more produced in alcohol bacterium；
Nitrogen-fixing bacteria are added in described retort；
In step (5), add methanol, carry out esterification in the presence of a catalyst, thus convert fatty acids step (4) produced is fatty acid methyl ester, isolates fatty acid methyl ester and alcohols, obtains alcohol-based fuel；
In step (5), add methanol, carry out esterification in the presence of a catalyst, thus be fatty acid methyl ester by the convert fatty acids that step (4) produces, isolating fatty acid methyl ester and alcohols, obtain alcohol-based fuel, methanol is (1.1-1.5) with the mol ratio of fatty acid: 1；
Described catalyst is solid super acid catalyst, and it is expressed as SO4 2-/SnO2-ZrO2-beta-molecular sieve, in this catalyst, Sn element is 8:1-15:1 with the mol ratio of Zr element；SnO2And ZrO2The weight ratio of gross weight and beta-molecular sieve be (1-10): (50-100), based on this catalyst cumulative volume L meter, sulfuric acid concentration i.e. SO in catalyst4 2-Concentration be 4.0-6.0mol/L；
Described beta-molecular sieve is Hydrogen beta-molecular sieve, and described beta-molecular sieve is the beta-molecular sieve being stripped of part framework aluminum, and the skeleton rate removing ratio of described beta-molecular sieve is 50-80%；
Described catalyst is prepared by the following method, weighs the SnCl of respective amount by above-mentioned mol ratio4∙5H2O、Zr(NO3)4∙4H2O is placed in container, adds deionized water wiring solution-forming, is subsequently adding beta-molecular sieve, is sufficiently stirred for dispersion and dipping；Under agitation being slowly added dropwise ammonia so that it is be co-precipitated, maintaining pH in whipping process is 7.5-8.0, then filters, is at room temperature aged 8-24 hour by precipitate；By precipitate washing, sucking filtration, dried, impregnating under agitation 2-5 hour with certain density sulfuric acid solution, then carry out filtering and being dried, finally carry out high-temperature calcination, described high-temperature calcination temperature is 300-600 DEG C, it is thus achieved that described solid super acid catalyst；
When using high-performance solid super acidic catalyst, catalyst is 1:500 to 1:2000 with the weight ratio of reactant methanol.
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