In the prior art, soy sauce is a kind of basic flavouring of the cooking, and the market demand is stably a large amount of, is used as production soy sauceWaste residue-soy sauce residues yield it is also very big.For a long time, it is believed that the industrial refuse that soy sauce residues, which are strange taste, to disturb residents, it is formerEasily putrid and deteriorated typically between 40~82% because being that soy sauce residues moisture is larger, long-distance transport is difficult.And normally give birth toThe enterprise of production soy sauce will produce substantial amounts of soy sauce waste residue daily, it is necessary to handle at once, otherwise, environmental pollution is extremely serious, specialIt is not summer, processing not in time, can produce strongly pungent acid smell, smokes to obtain people's dizziness, nausea.In addition, soy sauce residues are alsoWith certain toxicity, main cause is because salt content is higher in soy sauce residues about 10%, even as high as 25%, is not locatedThe soy sauce residues of reason are used as animal feed, and palatability is poor, Long-term Feeding or once feed amount excessively, easily cause salt poisoning, the lighterFeed falls sharply, weight loss, heavy then animal dead.Therefore, soy sauce residues are used for feed, are strictly controlled, consumption is few.How to haveEffect ground handles these " wastes ", thoroughly solves the situation that soy sauce waste residue strange taste disturbs residents, for a long time, and some area ground producers feelIt is very intractable.Therefore, how by soy sauce residues rationally using and not endanger the healthy of people be current urgent problem.
Biogas is a kind of fuel gas with higher thermal value, cleaning.With being continuously increased for biogas output, effectively, closeThe collection of reason, using, management method, efficiently turning into effectively control rural area using biogas, to face pollution, regenerated resources circulation sharpWith, promote agricultural and environment sustainable development provide technical support key.At present, the livestock and poultry breeding industry of China is especially supportedThe development of pig industry is swift and violent, and vast pig farm and wide farmers make full use of pork chop to put excrement development biogas industry.This biogas passes through pipeRoad provides combustion gas for kitchen use to wide farmers, and main kitchen fuel is turned into instead of natural gas, electric energy, a small number of to be also used to illuminateIt is used with marsh gas power generation.This common biogas, although property is similar to natural gas, but its CH4 content is 50~70%, it is otherImpurity CO2It is 0.2~3% for 20~30%, H2S, burning-point is 500 DEG C, caloric value is 20~25MJ/m3.Because common biogas containsH2S, therefore slightly have foul smell taste during burning, work as CH4During less than 45%, biogas could be lighted with naked light.Common biogas can onlyIt is civilian or for generating electricity, due to its CH4Content is low, and impurity is more, it is impossible to used as industrial methane.So, it would be highly desirable to find a kind ofPrepare methane content high, the method for the few biogas of impurity.
The content of the invention
The technical problems to be solved by the invention：Not disposable for existing soy sauce residues, pollution environment is extremely serious, andWith certain toxicity, improper use, harm people's is healthy, simultaneously because CH in the biogas of existing production4Content is low,Impurity is more, it is impossible to which there is provided a kind of method that utilization soy sauce residues prepare biogas for the problem of being used as industrial methane.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of method that biogas is prepared based on soy sauce residues, it is characterised in that specifically preparation process is：
（1）In mass ratio 1:3, take vermiculite and mass fraction to be put into for 10% hydrochloric acid in container, and container is placed in into ultrasonic shakeSwing in device, 40~50min is shaken with 1.6~1.9MHz, then filtering, filter residue is put into calcining furnace, design temperature is 1050~1100 DEG C, 1~2h is calcined, calcined material is collected；
（2）Count by weight, take 40~50 parts of wheat bran, 33~35 parts of rice husks, 22~26 parts of calcined materials and 4~6 parts of hydroxidesCalcium, is put into grinding mill and is milled, then mill admixture is crossed into 150 mesh sieves, collects sieving particle, you can obtain hybrid particles,It is standby；
（3）In mass ratio 1:3, soy sauce residues and mass fraction are put into mixer and stirred for 5% hydrogen peroxide, then by mixerMiddle mixture, which is put into filter press, carries out press filtration, collects filter cake；
（4）By filtration cakes torrefaction, crush, cross 100 mesh sieves, collect sieving particle, and the particle that will sieve is 30% with mass fractionEthanol solution is well mixed, and places into and steam blasting is carried out in steam blasting device, collects explosion thing, and the progress of explosion thing is coldIt is lyophilized dry, collect freeze-drying thing；
（5）Count by weight, take 60~70 parts of freeze-drying things, 23~26 parts of standby hybrid particles, 17~21 parts of additives,10~13 parts of water and 6~9 parts of calcium carbonate, are put into mixer and stir, and collect stirring mixture, obtain base-material；
（6）Base-material is put into methane-generating pit, design temperature is 32~35 DEG C, base-material is added into methane-generating pit within every 30~35 days, oftenSecondary base-material addition is the 30~40% of initial base-material addition, collects the gas that methane-generating pit is produced, you can obtain biogas.
The step（2）The mass ratio for the ethanol solution that middle sieving particle is 30% with mass fraction is 1:3~5.
The step（2）The temperature of middle steam blasting is 130~150 DEG C, and pressure is 1.7~1.9MPa, when maintaining pressureBetween 2~4min.
The step（2）8~12Pa of vacuum of freeze-drying, temperature is -50~-45 DEG C, 5~10min of drying time.
The step（4）The preparation method of middle additive is：Biogas slurry is filtered, filtered fluid, in mass ratio 1 is collected:2~1:4,200 mesh discarded mushroom bacterium rod particles are well mixed with filtered fluid, you can obtain additive.
The biogas slurry is pig biogas slurry.
The present invention is compared with other method, and advantageous effects are：
（1）The present invention is handled soy sauce residues by hydrogen peroxide first, the content of crude fibre inside reduction soy sauce residues, then withEthanol solution is mixed, and by Steam explosion treatment, improves the gas porosity and porosity of soy sauce residues, the battalion contained using insideForm point, then mix with self-control hybrid particles, additive, pass through hybrid particles and adjust nutrition composition, adjust fluffy degree, utilizationAdditive increases strain, and increase makes full use of to nutriment, adds the yield of biogas；
（2）The present invention prepares biogas using soy sauce residues, and soy sauce residues obtain great recycling, turned waste into wealth, and solve itThe problem of polluting environment；
（3）The production rate of methane prepared using soy sauce residues is high, and methane content and its calorific value are higher, have broad application prospects.
Embodiment
The preparation of hybrid particles：In mass ratio 1:3, take vermiculite and mass fraction to be put into for 10% hydrochloric acid in container, andContainer is placed in ultrasonator, 40~50min is shaken with 1.6~1.9MHz, then filtering, calcining furnace is put into by filter residueIn, design temperature is 1050~1100 DEG C, calcines 1~2h, collects calcined material；Count by weight, take 40~50 parts of wheat bran, 33~35 parts of rice husks, 22~26 parts of calcined materials and 4~6 parts of calcium hydroxides, are put into grinding mill and are milled, then by mill admixture150 mesh sieves are crossed, sieving particle are collected, you can obtain hybrid particles.
The preparation of additive：Pig biogas slurry is filtered, filtered fluid, in mass ratio 1 is collected:2~1:4,200 mesh are given upAbandon lentinus edodes strain stick particle to be well mixed with filtered fluid, you can obtain additive.
The preparation of biogas：Take soy sauce residues natural drying 3~4 days, in mass ratio 1:3, by the soy sauce residues and quality after dryingFraction is put into mixer for 5% hydrogen peroxide, stirs 3~5h with 180r/min, then mixture in mixer is put into press filtrationIn machine, press filtration is carried out with 20MPa, filter cake is collected；Filter cake is placed in 60 DEG C of drying boxes and dries 10~15h, then by dried filterCake is put into pulverizer and crushed, and crosses 100 mesh sieves, collects sieving particle, and will sieving particle and sieving granular mass 3~4Times mass fraction is well mixed for 30% ethanol solution, is put into steam blasting device, and design temperature is 130~150 DEG C, pressurePower is 1.7~1.9MPa, maintains 2~4min of pressure；After dimension pressure terminates, pressure release blowing collects explosion thing, and explosion thing is putEnter in vacuum freeze drier and be freeze-dried, set vacuum as 8~12Pa, temperature is -50~-45 DEG C, freeze-drying 5~10min, collects freeze-drying thing；Count by weight, take 60~70 parts of freeze-drying things, 23~26 parts of hybrid particles, 17~21 parts of additives, 10~13 parts of water and 6~9 parts of calcium carbonate, are put into mixer, and 1~3h is stirred with 300r/min, and collection is stirredMixture is mixed, base-material is obtained；Base-material is put into methane-generating pit, design temperature is 32~35 DEG C, is added into methane-generating pit within every 30~35 daysPlus base-material, each base-material addition is the 30~40% of initial base-material addition, collects the gas that methane-generating pit is produced, you can obtain natural pondGas.
Example 1
Take soy sauce residues natural drying first 4 days, in mass ratio 1:3, by the dioxygen that the soy sauce residues after drying and mass fraction are 5%Water is put into mixer, and 5h is stirred with 180r/min, then mixture in mixer is put into filter press, is pressed with 20MPaFilter, collects filter cake；Filter cake is placed in 60 DEG C of drying boxes and dries 15h, then dried filter cake is put into pulverizer crushed,100 mesh sieves are crossed, sieving particle is collected, and the particle that will sieve is mixed with sieving 4 times of mass fractions of particle matter for 30% ethanol solutionClose uniform, be put into steam blasting device, design temperature is 150 DEG C, and pressure is 1.9MPa, maintain pressure 4min；In dimension pressure knotShu Hou, pressure release blowing collects explosion thing, and explosion thing is put into vacuum freeze drier is freeze-dried, setting vacuumSpend for 12Pa, temperature is -45 DEG C, is freeze-dried 10min, collect freeze-drying thing；Count by weight, take 70 parts of freeze-dryingsThing, 26 parts of hybrid particles, 21 parts of additives, 13 parts of water and 9 parts of calcium carbonate, are put into mixer, and 3h is stirred with 300r/min, are receivedCollection stirring mixture, obtains base-material；Base-material is put into methane-generating pit, design temperature is 35 DEG C, base is added into methane-generating pit within every 35 daysMaterial, each base-material addition is the 40% of initial base-material addition, collects the gas that methane-generating pit is produced, you can obtain biogas.WhereinThe preparation method of hybrid particles is：In mass ratio 1:3, take vermiculite and mass fraction to be put into for 10% hydrochloric acid in container, and willContainer is placed in ultrasonator, shakes 50min with 1.9MHz, then filtering, filter residue is put into calcining furnace, design temperature is1100 DEG C, 2h is calcined, calcined material is collected；Count by weight, take 50 parts of wheat bran, 35 parts of rice husks, 26 parts of calcined materials and 6 parts of hydrogen-oxygensChange calcium, be put into grinding mill and milled, then mill admixture is crossed into 150 mesh sieves, collect the particle that sieves, you can must mixGrain.The preparation method of additive is：Pig biogas slurry is filtered, filtered fluid, in mass ratio 1 is collected:4, by the discarded perfume of 200 meshMushroom rod particle is well mixed with filtered fluid, you can obtain additive.
Its methane content, carbon dioxide content and aerogenesis situation are determined in collection biogas within the 25th day, 35 days and 45 days：
| Detection project | 25th day | 35th day | 45th day |
| Methane content（%） | 70.5 | 81.2 | 89.6 |
| Carbon dioxide（%） | 0.8 | 1.5 | 1.9 |
| Volume yield rate（m3·m-3·d-1） | 0.26 | 0.28 | 0.30 |
| High calorific power MJ/m3 | 33.5 | 36.2 | 37.8 |
Example 2
Take soy sauce residues natural drying first 3 days, in mass ratio 1:3, by the dioxygen that the soy sauce residues after drying and mass fraction are 5%Water is put into mixer, and 3h is stirred with 180r/min, then mixture in mixer is put into filter press, is pressed with 20MPaFilter, collects filter cake；Filter cake is placed in 60 DEG C of drying boxes and dries 10h, then dried filter cake is put into pulverizer crushed,100 mesh sieves are crossed, sieving particle, and the ethanol solution for being 30% by the 3 times of mass fractions of particle and sieving granular mass that sieve is collectedIt is well mixed, it is put into steam blasting device, design temperature is 130 DEG C, and pressure is 1.7MPa, maintains pressure 2min；In dimension pressureAfter end, pressure release blowing collects explosion thing, and explosion thing is put into vacuum freeze drier is freeze-dried, and setting is veryReciprocal of duty cycle is 8Pa, and temperature is -50 DEG C, is freeze-dried 5min, collects freeze-drying thing；Count by weight, take 60 parts of freeze-dryingsThing, 23 parts of hybrid particles, 17 parts of additives, 10 parts of water and 6 parts of calcium carbonate, are put into mixer, and 1h is stirred with 300r/min, are receivedCollection stirring mixture, obtains base-material；Base-material is put into methane-generating pit, design temperature is 32 DEG C, base is added into methane-generating pit within every 30 daysMaterial, each base-material addition is the 30% of initial base-material addition, collects the gas that methane-generating pit is produced, you can obtain biogas.WhereinThe preparation method of hybrid particles is：In mass ratio 1:3, take vermiculite and mass fraction to be put into for 10% hydrochloric acid in container, and willContainer is placed in ultrasonator, shakes 40min with 1.6MHz, then filtering, filter residue is put into calcining furnace, design temperature is1050 DEG C, 1h is calcined, calcined material is collected；Count by weight, take 40 parts of wheat bran, 33 parts of rice husks, 22 parts of calcined materials and 4 parts of hydrogen-oxygensChange calcium, be put into grinding mill and milled, then mill admixture is crossed into 150 mesh sieves, collect the particle that sieves, you can must mixGrain.The preparation method of additive is：Pig biogas slurry is filtered, filtered fluid, in mass ratio 1 is collected:2, by the discarded perfume of 200 meshMushroom rod particle is well mixed with filtered fluid, you can obtain additive.
Its methane content, carbon dioxide content and aerogenesis situation are determined in collection biogas within the 15th day, 25 days and 35 days：
| Detection project | 15th day | 25th day | 35th day |
| Methane content（%） | 68.9 | 70.8 | 85.6 |
| Carbon dioxide（%） | 0.7 | 1.2 | 1.6 |
| Volume yield rate（m3·m-3·d-1） | 0.28 | 0.29 | 0.32 |
| High calorific power MJ/m3 | 37.5 | 35.2 | 36.8 |
Example 3
Take soy sauce residues natural drying first 3 days, in mass ratio 1:3, by the dioxygen that the soy sauce residues after drying and mass fraction are 5%Water is put into mixer, and 4h is stirred with 180r/min, then mixture in mixer is put into filter press, is pressed with 20MPaFilter, collects filter cake；Filter cake is placed in 60 DEG C of drying boxes and dries 12h, then dried filter cake is put into pulverizer crushed,100 mesh sieves are crossed, sieving particle, and the ethanol solution for being 30% by the 3 times of mass fractions of particle and sieving granular mass that sieve is collectedIt is well mixed, it is put into steam blasting device, design temperature is 140 DEG C, and pressure is 1.8MPa, maintains pressure 3min；In dimension pressureAfter end, pressure release blowing collects explosion thing, and explosion thing is put into vacuum freeze drier is freeze-dried, and setting is veryReciprocal of duty cycle is 10Pa, and temperature is -47 DEG C, is freeze-dried 7min, collects freeze-drying thing；Count by weight, take 65 parts of freezings dryDry thing, 25 parts of hybrid particles, 20 parts of additives, 12 parts of water and 8 parts of calcium carbonate, are put into mixer, and 2h is stirred with 300r/min,Stirring mixture is collected, base-material is obtained；Base-material is put into methane-generating pit, design temperature is 33 DEG C, added into methane-generating pit within every 33 daysBase-material, each base-material addition is the 35% of initial base-material addition, collects the gas that methane-generating pit is produced, you can obtain biogas.ItsThe preparation method of middle hybrid particles is：In mass ratio 1:3, take vermiculite and mass fraction to be put into for 10% hydrochloric acid in container, andContainer is placed in ultrasonator, 45min is shaken with 1.8MHz, then filtering, filter residue is put into calcining furnace, design temperatureFor 1070 DEG C, 1h is calcined, calcined material is collected；Count by weight, take 45 parts of wheat bran, 34 parts of rice husks, 25 parts of calcined materials and 5 parts of hydrogenCalcium oxide, is put into grinding mill and is milled, then mill admixture crossed into 150 mesh sieves, collects sieving particle, you can must be mixedGrain.The preparation method of additive is：Biogas slurry is filtered, filtered fluid, in mass ratio 1 is collected:3, by 200 mesh discarded mushroom bacteriumRod particle is well mixed with filtered fluid, you can obtain additive.Wherein biogas slurry is pig biogas slurry.
Its methane content, carbon dioxide content and aerogenesis situation are determined in collection biogas within the 5th day, 10 days and 15 days：
| Detection project | 5th day | 10th day | 15th day |
| Methane content（%） | 69.3 | 74.5 | 89.3 |
| Carbon dioxide（%） | 0.6 | 1.0 | 1.2 |
| Volume yield rate（m3·m-3·d-1） | 0.30 | 0.28 | 0.23 |
| High calorific power MJ/m3 | 39.5 | 34.2 | 39.8 |
Above-described embodiment is not limited for the present invention preferably embodiment, but embodiments of the present invention by above-described embodimentSystem, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,Equivalent substitute mode is should be, is included within protection scope of the present invention.