CN104245164B - The method reclaiming humus from the transudate deriving from urban solid garbage field etc. - Google Patents

Abstract

A kind of during the maturation stage that pH value is 7.0 10.0, the method reclaiming humus from the transudate deriving from urban solid garbage field etc., it is characterized in that: at the temperature of 50 130 DEG C and the pressure of 5 200kPa, make this transudate through evaporative concentration stage of saline, the concentration transudate acidified stage containing this material in the solution will be made with mineral acid, reach pH value 13, to obtain the humus precipitation of fluffy solid form, separate to obtain raw humus from liquid phase by cotton-shaped humus solid.

Description

The method reclaiming humus from the transudate deriving from urban solid garbage field etc.

Technical field

The present invention relates to a kind of method reclaiming humus from the transudate deriving from urban solid garbage field etc. and The humus obtained by the method.

Background technology

Humus is complicated organic substance, that it has a change and still do not have the clearest and the most definite structure (supramolecular, The structure of macromole), it is made up of the branched chain of main but non-exclusive monocycle and the aromatic hydrocarbons of multi-ring (including heterocycle), mainly has Carboxyl, phenol and hydroxy functional group, also ether, ester, amino etc..

As follows, these materials according to them in different pH value (acid ph value 0-7, pH neutral 7, alkaline ph values " dissolubility " (more accurately, they form the ability of colloidal state " colloidal sol ") in water 7-14) classifies:

-humic acid (HA) is insoluble at acid ph value and solvable in alkaline ph values

-Fulvinic acid(a necic acid) (FA) is at acid ph value and solvable in alkaline ph values

-humin is at acid ph value and insoluble in alkaline ph values

These dissolubility properties make humus can extract from carbonate minerals such as leonardite, brown coal, mud coal, with And the extraction from following compound being recently proposed: this compound is by converting and stablizing debirs example in controlled equipment Organic moiety such as solid municipal waste (S.U.R) produces.

The leonardite formed in the slowly decomposition of organic substance (particularly lignin) is planting in mud coal and brown coal The phase of the nearest surface oxidation that the geochemistry of thing organic substance converts.It is especially rich in humus, and it is in alkaline aqueous solution Extract with potassium hydroxide (pH value 9-12).These solution (it can comprise the inorganic salt dissolving in alkaline water with variable) lead to Often sell according to derived region, there is different humus concentration, especially as the soil improver in agricultural.This side Face, humus is by soil treatment and is changed soil characteristic by foliage applying (leaf application) and improves The growth of major part different crops and health.

Specifically, humus improves:

-retention capacity of soil；

-Soil structure and fertilizer degree；Due to the chelating effect of functional group present in humus, it is therefore prevented that nutrient substance and micro- Secondary element (ferrum, calcium, phosphorus etc.) is washed off, and their utilizability increases in time, thus the growth of beneficially plant And health.

Humus is the most biological nondegradable；(FA) and big point of high molecular (HA) in they consist of Son, has hydrophobic part and a hydrophilic functional groups (it is partially acidic), and is the salifie form of they and alkalinous metal, table Revealing surfactant properties, this makes them can also act as the surfactant in earth and soil cleaning, because passing through Their chelating ability is also used to be used for them removing hydrocarbon and/or heavy metal in different heavy metals.

Obtained by the controlled oxidation of coal and be similar to humus, but the material of non-natural origin, and carried Go out as soil improver or for the industrial ash rich in heavy metal is carried out deactivation.

Known according to refuse quality and rubbish amount of cure and rainfall level, the transudate from S.U.R. rubbish can comprise Humic quality (0.05-5 weight %), it is considered as interesting in industry and commercial object；But by known Method directly reclaims them from transudate can not obtain product with competitive cost, and this product does not has in transudate Various pollutant, especially relate to nitridation and containing the compound of ammonia, be therefore unsuitable for being similar to be obtained by preceding method The purposes of the humus obtained.

Summary of the invention

It is an object of the present invention to provide a kind of method, it can obtain with the transudate of similar refuse from S.U.R. rubbish Can the humus of sales volume, be simultaneously achieved reagent (acid, additive) less consumption and use simple technique, it can be whole Close and use prior art, realizing low investment and operating cost.

In order to reach this target, it is necessary to consider following content.

Humus concentration in transudate changed along with the time (age) of S.U.R. rubbish activity；Known continuous print is raw Thing degradation period (once toppling over, i.e. occur on the organic component of refuse) is as follows:

The aerobic biological degradation of-initial temporary stage, this is mainly due to the oxygen in gap, produces little during this period Transudate or humus；

The anaerobic degradation of the-the second long periods, itself is divided into following successive stages:

A) give birth to acid phase, wherein form volatile fatty acid and carbon dioxide by fermentation, and pH value reduces subsequently.? Acid ph value (5-6) defines a large amount of transudate, and it has high BOD₅, high salt concentration, mobility of heavy metals, but exist relatively low Humus；

B) generating the acetic acid stage, wherein define volatile short chain acid by fermentation, they enter by generating acetic acid bacteria One step is degraded into acetic acid, the substrate of methane-producing bacteria.Create methane, reduce hydrogen and carbon dioxide, and pH value increases.This oozes Go out liquid and there is the metal lower than earlier stage and BOD₅Concentration, and increase humus and ammonia density；

C) methane phase is generated, wherein by (hydrogenophilic) of hydrogen methanogenic, close that be dominant and especially Parent (acetophilic) antibacterial of acetyl and form methane (methane of 70% thus generates) in a large number.The feature in this stage exists In rubbish " ripening ": transudate has neutral-alkaline pH value (7-10)；Low volatile acid and the solid concentration of dissolving are (low BOD₅), low heavy metal (such as Fe, Zn) activeness, high ammonia density, maximum humus concentration.

From the transudate of " ripening " rubbish actually by its humus typical dark-brown (HA brown-black；FA Yellow-brown) can visual identification.By physico-chemical analysis (spectrogrph, UV, FTIR, NMR etc.) available from different S.U.R. rubbish The chemistry carried out on the humus of transudate and structural property are studied it has been shown that they are similar to, but be not equal to by from In leonardite, mud coal, brown coal, compost extract and obtain those.

In the purification to rubbish transudate, humus mainly together with the hydroxide of heavy metal and subcarbonate, By with aluminum and iron salt, calcium hydroxide, organic coagulant etc., carrying out precipitating/clarify wadding by membrane technology skill (ultrafiltration, reverse osmosis) Coagulate and remove, but this film is easily blocked by humus.This transudate purifies produced mud and is typically recycled to soot Or otherwise dispose, it for reclaim enough commercial qualities humus for be not economy easily.

" ripening " transudate has been alkalescence humus solution, and is divided into generally according to Italy and European directive " transudate refuse, specific benign " (CER code 190703).Additionally provide a kind of feasible inceptive filtering to guarantee to appoint What " solid of suspension " is in low-level, less than 500mg/L, organic trace contaminant of some danger known such as polychlorostyrene hexichol And two English and polychlorostyrene dibenzofurans (if present) be almost adsorbed onto in particulate matter (suspended solid).

It is an object of the present invention to reclaim humus from this solution, and purify any pollutant (its that they are existing Make them unsuitable for each particular use).

If in the present invention it has been found that by with the ripening transudate of mineral acid such as sulfuric acid treatment pH value 7-10 until Precipitate completely at pH value 2-2.5 humus, replace with and the most under vacuo transudate is being concentrated 10-20 take second place by evaporation After, this transudate carries out identical operation, then it is enough for using following mineral acid quantity: this amount is identical equal in process During the transudate of non-concentrated of amount 1/4th of amount used.This concrete acid consume be reduced to about 1/4th be by During concentration processes, significantly reduce what the basicity of transudate realized, this is because generally with high concentration in ripening transudate The bicarbonate particularly ammonium hydrogen carbonate thermal decomposition ammonification existed and carbon dioxide, then it removed from transudate by evaporation Go.

Another advantage carrying out humus Acid precipitation on the transudate being such as concentrated under vacuum by evaporation is dense Contracting transudate and therefore the most there is not possible volatile contaminant in the humus therefrom precipitated, either has Machine (carboxylic acid, hydrocarbon, other aliphatic series/aromatics organic substance, including halo and nitridation) or inorganic (mainly ammonia)；This Promote humus cleansing phase subsequently, to obtain the humus of commercial quality.

Another advantage is can to ooze out in the concentration discharged from vaporizer at 50-100 DEG C in the stage of humus Acid precipitation The temperature heat of liquid is carried out, and without other cost of energy, thus improve the efficiency of precipitate morphology and subsequent stage: Gu- Liquid separate and with water (possibility with mineral acid acidified to pH value < 7) cleaning, reducing impurity such as inorganic salt and water solublity has Machine compound.

Being in evaporation process concentrating another advantage of operation on transudate, it have passed through at the heat of 50-130 DEG C of temperature Reason lasts high mean residence time (2-7 hour), and reduces initial bacteria load capacity subsequently, and this is also being acidified to pH value 2 Next stage in reduce further, it is thus achieved that there is no dangerous bacteria such as escherichia coli (Escherichia coli) Product with Salmonella (salmonella).

Finally, except favourable economic implications (humus is a kind of value product, its except aforementioned exercise use it Outward, other gainful application also can be found in future) outside, the present invention also has sizable environmental effect, and this is Because it reclaims the most economic compatible material from refuse, this material is particularly useful for reclaiming and improve barren and/or stream The soil lost, this is conducive to carbon dioxide conversion to become to be intended for use food purpose or for forming the plant life of regenerative resource Material, and reduce the discharge to air of this greenhouse gases subsequently.

This target is according to the present invention, by reclaiming humus from the transudate deriving from urban solid garbage field etc. Method realizes.

Accompanying drawing explanation

Fig. 1 shows the process chart of the present invention.

Detailed description of the invention

Following by with reference to attached block diagram and some embodiments of being given as non-limiting example, clearer The preferred embodiments of the invention.

From this block diagram, in the method for the invention, if derive from the transudate in S.U.R. soot etc. it When " ripening " stage comprises the solid of suspension, at the beginning of coming with suitable filter such as sand filter, microstrainer, decanter, centrifuge Begin to filter it, to obtain " solid of the suspension " concentration less than 500mg/L (being measured by IRSA-CNR 2090 method), remove Remove any pollutant organic substance such as polychlorostyrene dibenzo two English and polychlorostyrene dibenzofurans, it is known that they (if there is Words) can be adsorbed onto in the solid particle of suspension.

Concrete transudate has neutrality or alkaline ph values (pH value 7-10), and color is brown, comprises more than 0.1 weight % Organic substance, this is by the dry residue (R105) of 105 DEG C and difference between the dry residue (R600) of 600 DEG C, Utilizing IRSA Q64 (2) 84met.02 method to measure, the humic carbon of particularly greater than 0.05 weight %, this passes through DM 23- 01-91S.O.G.U No.29/91 method measures.

Transudate the most under vacuo at the pressure of 5-200KPa, the temperature of 50-130 DEG C through continuous print evaporation stage, Preferably by continuous print multiple-effect method, mean residence time 2-7 hour, until obtaining liquid residue, its volume is reduced to In the 1/5-1/29 of initial transudate volume, and it is in alkaline ph values 8-11.

The transudate concentrated comprises the whole humus being in solution, particularly solvable in alkaline environment humic Acid, Fulvinic acid(a necic acid) and inorganic salt, particularly chloride, sulfate, phosphate, alkali silicate (Na, K salt) and alkaline-earth metal Silicate (Ca, Mg salt).

The condensed water in evaporation-concentration stage comprises present in initial transudate all volatile contaminants, such as ammonia, waves The property sent out organic substance, hydrocarbon, the organic substance of halo.These materials eliminate in stripping/absorption stage subsequently from condensed water, This stage also is able to reclaim ammonium sulfate, and this is industrial viable.The condensed water purified in this way may be used for thick corruption Grow in matter acid wash phase, or such as being aoxidized by known method, be adsorbed onto on activated carbon, ultrafiltration, reverse osmosis etc. are entered The further purification of line option, after obtaining the pollution limit allowing discharge, is discharged to public sewer, surface water or soil In.

Temperature between ambient temperature to the boiling point of concentration transudate, under agitation, sinks at discontinuous or continuous print In shallow lake device (such as three grades), add the concentrated sulphuric acid of aqueous solutions of organic acids such as 37.5 weight %, the hydrochloric acid of 37.5 weight %, 75 weights The phosphoric acid of amount % makes transudate acidified stage of concentration, and under ph control and under agitation, such as by using Static mixer is recycled for acid carries out continuous pipe distribution (line dispensing), until cotton-shaped humus solid exists PH value 1-3, the most stable (constant) 2.0 precipitates completely；Required acid amount is different along with transudate type and acids type: example As for ripening transudate, for the sulphuric acid of 37.5 weight %, it can be about 10 bodies of the transudate volume concentrated Long-pending %.

Humus starts precipitation at pH value 4.5-4.0, and is likely to be formed foam, and it can be by adding a small amount of froth breaking Agent (such as organic silicon type) reduces and controls；Acidifying and settling system have agitating device, for release and process steam and Not condensables such as carbon dioxide, hydrogen sulfide and under described pH value and temperature conditions volatile weak inorganic and organic acid thing The device of matter；Therefore, this stage also from humus purification can reduce the material of they qualities, such as there is unhappy abnormal smells from the patient Dangerous sulfide.

Humus is then passed through the solid/liquid separation stage realized by one or more known methods, such as, filter, including Vacuum filtration, centrifugation, decant, flotation etc..In order to improve the efficiency of these operations, can add a small amount of, logical aptly The often less than polymer flocculants such as polyacrylate of 1.0 volume %, polyacrylamide base cationic polyelectrolyte, adds Agent (it affects final product quality in no instance).

At the end of these stages, it is thus achieved that below:

The acid solution of the inorganic salt of-pH value 1-3, preferably 2.0, its amount is the suspension obtained previously by acidifying 20-90 volume %, its Fulvinic acid(a necic acid) (yellow) containing the part being present in initial transudate and other water dissolvables are non- Volatile organic matter；This solution is supplied to the pH value neutral zone more than 4, then disposes or be supplied to concentrate and crystallization Stage separates (especially by precipitation) alkalescence and heavy metallic salt, mainly chloride and sulfate, is returned by condensed water simultaneously Receive and be recycled to next cleaning area or send to discharge after optional process.

The sour suspension of the concentration of the raw humus of-pH value 1-3, preferably 2.0, its amount is previously by oozing that acidifying concentrates Go out the 80-10 volume % of the raw humus suspension that liquid is obtained, and there is at 105 DEG C 10-80 weight % of raw humus Dry residue, it is mainly made up of humic acid and less amount of Fulvinic acid(a necic acid).Then by adding alkaline hydrated oxide, preferably The aqueous solution of potassium hydroxide reach pH value 5.0-10.0, preferable ph 7.0 and make raw humus as soluble alkali humic acid Salt dissolves；Creating raw humus aqueous solution, its (can be diluted) can meet by current in qualitative and quantitative testing After the analytical limits that regulation provides, as the soil improver in agricultural, the described regulation product for similar source is such as Come from municipal administration flow out the mud of water purifier and come from the compost of S.U.R. organic moiety.

If it is considered to necessary, then before with the aqueous dissolution of alkaline hydrated oxide, raw humus use water is cleaned clean Changing, described water is probably derived from the evaporation stage of this method the purification (Fig. 1) of produced condensate, and it uses mineral acid example Such as sulphuric acid and/or hydrochloric acid and/or phosphoric acid, to pH value, < 7, all circulated by known method or continuous print cleans OK.

Obtain the suspension of the humus of purification, its 105 DEG C have 10-80 weight %, preferably 40 weight % dry Residue, pH value is 5-7, and has Low-salinity, is expressed as at 600 DEG C less than 15 weight %, the dry residual of preferably 5 weight % Thing.

If it is considered to necessary, then the raw humus dissolved as alkalescence humate or the aqueous solution of the humus of purification can By known treatment, to purify further with solid absorbent product such as activated carbon, Kaolin, clay etc., to remove any Organic trace contaminant such as alkyl phthalates, particularly phthalic acid 2-ethyl-own ester, nonyl-and octyl group- Phenol, bisphenol-A.

Above-mentioned raw humus or the aqueous solution of the humus of purification, except, after optional dilution, meeting regulation institute During qualitative the and determination limit provided as soil improver outside the crop of agricultural, it is also possible to change into by different way Following form (its be similar on humus market existing those):

-powder or partical, water content is 10-30 weight %, its by be dried obtain, such as in wastewater disposal basin and expose It is exposed to air, electric furnace or microwave oven, infrared ray etc.,

-as the product of ferric humate (II) solution, it obtains by adding ferrous sulfate to alkaline solution,

The suspension of-calcium humate or magnesium or dry product, it is by adding CaO, Ca (OH)₂Or MgO or Mg (OH)₂ Reach pH value > 7, the precipitation of insolubilized humic acid calcium or magnesium during alkaline ph values obtain.

The present invention will be described for the following examples, but and its scope unrestricted.

Embodiment 1)

Under ambient temperature and continuous stirring, by 37.45 weight % aqueous sulfuric acid (density of continuous increment (ml) 1.28g/ml) add the transudate former state (sample 1p) of the filtration of the 100ml deriving from " ripening " S.U.R. soot (A) to In, it has the suspended solid less than 500mg/l, dark-brown, has the characteristic shown in table 1, simultaneously with the glass with correction The pH meter of electrode measures pH value, and have recorded the value that each subacid adds when constant pH.

Observe bubbling time initial, and produce foam, by adding the organic silicon defoamer (10%Dinapan of 0.2ml 16WD solution) it is reduced and controls.Cotton-shaped brown precipitate, and the face of this solution is initially formed when about pH value 4 Color becomes clarification, bubbling and foaming towards yellow and stops, and continues to add sulphuric acid.

When pH value is 2 stop add sulphuric acid, and by a part suspension be placed in test tube, and 3200rpm from The heart separates 10 minutes, is separated by the supernatant of settled solution form.It is added to sulphuric acid；Do not observe other precipitation shape Becoming, therefore precipitation is considered substantially to terminate.By whole products of being obtained in suitable laboratory equlpment 3200rpm from The heart separates 10 minutes, and is separated with precipitate by the supernatant of clarification, and bottom suspension is made up of 10g humidity raw humus (sample HS1), has the chemical characteristic that table 2 provides.

Table 3 shows for described sample (1p), the amount that 37.45 weight % sulphuric acid of interpolation are expressed with volume and weight and The pH value obtained after each time is added；When pH value 2.2, every 100ml transudate former state uses the bright sulfur acid of 1.97g (20.1mgmol)。

Transudate described in 2000ml (sample 1p) is such as concentration of getting off: 70 DEG C of temperature in Rotavapor laboratory equlpment With under vacuum, at the pressure evaporating about 3 hours of 46KPa, until reaching volume to be reduced to 1/11st, to obtain the dark brown of 182ml The transudate (sample 1pc has the characteristic of table 1) of the concentration of color and the aqueous condensate of 1818ml.It is being cooled to ambient temperature After, in an identical manner a certain amount of sulphuric acid is added to the transudate of the concentration of 100ml, sample 1pc (oozes corresponding to 1100ml Go out liquid former state) in, and pH value determination, until humus precipitation terminates, and it is existing to have the observation identical with aforementioned sample 1p As；After centrifugation, it is thus achieved that the moist raw humus (sample HS1c) of 41.8g, it has the characteristic that table 2 provides.

Table 3 shows for following, relative to volume (ml) and the weight (g) of the sulphuric acid used by pH value:

1) sample 1p/100ml transudate former state；

2) sample 1pc/100ml is concentrated into the transudate (corresponding to 1100ml transudate former state) of 1/11st；

3) sample 1pc, it normalizes to 100ml transudate former state (corresponding to the transudate of concentration of 9.09ml).

This compares display, and the transudate (1pc) concentrated based on 100ml employs 5.71g (5.82mgmol) sulphuric acid, its warp Calculate the transudate former state before concentrating corresponding to 0.519g (5.29mgmol) sulphuric acid/100ml；And for unconcentrated sample (sample Product 1p), need 1.97g (20.1mgmol) sulphuric acid/100ml transudate former state (sample 1p) of much higher amount, on this consumes Add about 3.7 times.

Table 2 shows the difference between the chemical characteristic of these two kinds of samples, specifically, product (sample HS1c) table of concentration Reveal the higher dry residue at 105 DEG C, 23.50%, good humic and the mould carbon of sallow (fulvic carbon) level, Low-level heavy metal and high-caliber soluble alkali salt (sodium, potassium), it may be reduced by cleaning subsequently.

This embodiment highlights the novelty of the present invention, and it is that the transudate in the concentration obtained by thermal evaporation is enterprising The Acid precipitation of row innovation, it is achieved that the important reduction of required acid amount, thus produces economic advantages.

About transudate former state (sample 1p) and relative enhancement thing (sample 1pc) by the possible dirt of dangerous organic compound Dye, also finds following by enough sensitivity and specific conventional method of analysis in these samples:

-Polychlorinated biphenyls (PCB)；

-aromatic polycyclic hydrocarbons (APH) (naphthalene, benzo (e) pyrene, acenaphthylene, acenaphthene, fluorine, phenanthrene, pyrene, benzo (a) anthracene, bend (chrysene), benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, indeno (123cd) pyrene, dibenzo (ah) anthracene, benzo (ghi), dibenzo (al) pyrene, dibenzo (ae) pyrene, dibenzo (ai) pyrene, dibenzo (ae) pyrene)；

-carcinogenic halogenated aliphatics (bromofom, 1,2-methylene bromide, dichlorodibromomethane, bromodichloromethane)；

Chlorinated aliphatic compound (1,1-dichloroethanes, 1,2-dichloroethanes, 1,1,1-trichloroethane, the 1,2-of-non-carcinogenic Dichloropropane, 1,1,2-trichloroethane, 1,2,2-trichloropropane, 1,1,2,2-sym-tetrachloroethane)；

-carcinogenic chlorinated aliphatic compound (chloromethanes, dichloromethane, chloroform, vinyl chloride, 1,2-dichloroethanes, 1,1-bis- Vinyl chloride, trichloro ethylene, tetrachloroethylene)；

-chloroaromatic compounds (chlorobenzene, 1,2-dichloro-benzenes, 1,4-dichloro-benzenes, 1,2,4-trichloro-benzenes)；

-aromatic organic solvent (benzene, toluene, ethylbenzene, styrene, dimethylbenzene, isopropylbenzene).

The correlated results of whole aforementioned organic compound be content be less than the 1mg/kg of this analysis method can measuring range. Following again smaller than respective analysis measuring range:

-total hydrocarbon (< 10mg/kg)；

-C < 12 hydrocarbon (< 5mg/kg)；

-C>12 hydrocarbon (<5mg/kg).

Therefore, even after being concentrated into 1/11st, " ripening " rubbish transudate (A) does not the most demonstrate described danger The pollution of the provision discussion measuring range of organic compound.

Embodiment 2)

By the embodiment 1 of 2000ml) " ripening " rubbish transudate (A) in the lab with embodiment 1) identical side Method, temperature and pressure concentrate, with obtain 166ml be concentrated into 1/12nd transudate (sample 2pc).

Under agitation in ambient temperature to 75 weight % phosphoric acid (d:1.5) of continuous quantity are added the described of 100ml part In the transudate concentrated, pH value determination the most continuously, as in the previous embodiments；Table 4 shows concentration based on 100ml Transudate, relative to the amount of the volume and weight (ml and g) of pH value, and the amount of 8ml concentrate is unconcentrated corresponding to 100ml Transudate former state.

Visible such as embodiment 1), humus starts precipitation at pH value 4.4 and terminates at pH value 2.3；Phosphoric acid used It is transudate and the 11.48mgmol/100ml transudate former state of 143mgmol/100ml concentration.

In order to improve sedimentary filterability, add coagulant solution Hydrapol C180 (80mg/100ml) to it In, the most after agitation this mixture is filtered by filter paper (black vaginal discharge) (residual pressure 0.8KPa) under vacuo；For The transudate of the concentration of 31.7%w/w, it is thus achieved that moist humus, and at 105 DEG C (R105), there is the dry of 26 weight % Dry residue.

Phosphoric acid is used to be obtained in that, containing phosphatic humus, it is typically used as the fertilizer in agricultural, therefore, it is possible to make Obtain the raw material increment used by the present invention.

Embodiment 3)

Using the transudate of industry concentration, it is by the equipment of operation in " ripening " rubbish (B), and heat is steamed under vacuo Send acquisition, there is features below:

Transudate described in 200ml (sample 3pc) is heated to 65 DEG C, and simulating can by acidifying in concentrator outlet temperature Can precipitation, then by sample keep heating while, by 37.45 weight % sulphuric acid of gradually increment with embodiment 1) phase Same mode is added, the most continuously pH value determination, and its pH value at the end of precipitation is 2.2；Need 22ml sulphuric acid (equal to 11 bodies The transudate of the concentration of long-pending %).

Table 5 shows that 37.45 weight % sulphuric acid in the transudate (sample 3pc) of the concentration adding 100ml to are with volume The amount expressed with weight and the pH value obtained after each interpolation；Altogether need the transudate that 53.8mgmol/100ml concentrates, Be very similar in embodiment 1) in the value of transudate of the different concentration of 58.2mgmol/100ml that finds.

Thick moist humus (the sample 3pc of 7.1 weight %) is entered by centrifugation from the suspension obtained Row separates, such as embodiment 1), and 105 DEG C of dry residues: 28.9 weight %；600 DEG C of dry residues: 17.1 weight %； (R105-R600): 10.8 weight %.

Supernatant (the yellow-brown solution of clarification) is 92.9 weight %, and R105:14.67 weight % and R600: 12.5 weight %；(R105-R600): 2.17 weight %.

The efficiency purified from soluble-salt for washing of upchecking, that adds equal quantities (weight ratio 1/1) uses sulphuric acid It is acidified to the water of pH value 1；After by stirring normal mixing, use centrifugation to come from cleaned humus precipitate and divide From the supernatant being made up of the yellow solution clarified；R105；R600；Chloride；Two parts are all measured by sulfate；With continuously Order carried out four times clean.

Table 6 shows analysis result, from which it can be observed that

-in supernatant, for cleaning every time, cleaning based on 1/1 weight ratio, the amount of extraction decreases about 50 weights Amount %；After cleaning the 4th, the value measured is reduced to about the 10% of initial value, and this shows to make for extracting soluble-salt The ability that people is satisfied；

-in the humus of precipitation, it can be seen that when the 4th cleans, R105 decreases 10.7 weight %；R600 decreases 10.4 weight %, and organic substance (R105-R600) is 11.5 weight %, the most unchanged.These results confirm passes through water Washing the facility purifying humus from soluble-salt can be more preferably when acidifying.In the process system of a kind of integration, can make With the water of the condensate deriving from hot enriching stage, including under vacuo, as shown in the process chart of Fig. 1.

Embodiment 4)

By embodiment 1) used by 20ml organosilicon defoaming solution under agitation add to 25kg industry concentrate ooze out In liquid (sample 4pc), this transudate derive from embodiment 3) equipment that runs of identical rubbish (B), but be in difference Period, there is features below:

Further, while slowly checking bubbling and relative foaming, 37.45 weight % sulphuric acid of 20 DEG C of interpolation 2.7L Reach pH value 2.1；Obtain dark-brown flocculent deposit, be added to the Idrapol C180 flocculating agent of 25g；This product is existed Stirring is lower to keep 1 hour, is then filtered by non-woven polypropylene cloth (Polyfelt TS20 type (4.01)) by gravity, Separate described precipitate and obtain the thick moist humus of 2.5kg.

Take out the thick moist humus of 10g part, and with water (being acidified to pH value 1 with sulphuric acid) with raw humus/water The ratio of 1/1v/v is carried out, centrifugation subsequently and sediment separate out；Carry out altogether cleaning for four times with continuous print step, come clean Change water soluble salt.Obtain purified humus sample (sample HS4).Table 7 gives the analysis result of sample HS4 (with weight Amount % expresses, based at the dry residue of 105 DEG C) and method used.Specifically, it can be observed that residual the high level cadre of 600 DEG C Stay thing and high calcium (Ca) content (9.5 weight %) and high-sulfate (SO₄) content (30.5 weight %), mol ratio (0.7:1) Guarantee to exist mostly as calcium sulfate (CaSO₄) sulfate ion (SO₄)。

The composition (partially rendering below) of sample HS4 is characterised by chloride (Cl), sodium (Na) and the potassium (K) reduced Content:

Therefore visible by being acidified with sulphuric acid, add this humus, also precipitate alkali earth metal sulfate, particularly sulphuric acid Calcium and colloidal silica.These compounds are insoluble in the water (being acidified to pH value 1 with sulphuric acid) for cleaning, and alkali is golden The chloride (Cl) belonging to salt, particularly sodium (Na) and potassium (K) exists with the total concentration less than 1%.

It can be seen that calcium sulfate (CaSO₄) and colloidal silica (SiO₂) used also as the soil improver in agricultural and Soil pH value correction agent (calcium sulfate)；Therefore by the transudate rich in calcium, mix by using identical technique can obtain product Compound, it can play several useful function in agricultural.

By the sample HS4 of fraction in stove at the air drying 2 hours of 105 DEG C to constant weight；By about 0.6g with about The potassium bromide (KBr) of 200mg is used in mixed way, and tablet is made in compression；FT-IR spectrum is obtained based on the latter, and with By identical method by the KBr sheet made by the commercially available humus sample extracted from leonardite (COM2) and standard calcium sulfate The spectrum of agent compares.This spectrum compares display, there is commercially available humus (COM2) and the Absorption Characteristics of calcium sulfate simultaneously Bands of a spectrum, which demonstrate the latter and are present in sample HS4.

About the pollution possible by dangerous non-VOC, the most visible, even at rubbish transudate (B) and in purified humus, those major parts found do not exist with the concentration limited the quantity more than analysis method, institute The existence concentration of those found purifies mud as agricultural soil modifier about using at present less than Italy and Europe Regulation limit, and especially relate to trace contaminant such as polychlorostyrene dibenzo two English/furan (PCDD/PCDF), adjacent benzene Dioctyl phthalate 2-ethyl-own ester, aromatic polycyclic hydrocarbons (APH), Polychlorinated biphenyls (PCB).

Finally, with regard in the transudate of concentration obtained by it in rubbish transudate (B), by evaporation and purified corruption Growing the biological pollution in matter HS4, the total coliform concentration found 18000UFC/100ml from transudate changes to dense < 1UFC/100ml in the transudate of contracting and purified humus HS4.Which demonstrate by thermal evaporation under high temperature and vacuum The transudate method for concentration carried out is effective carrying out disinfection the transudate concentrated.Another of the humus sterilization of precipitation is protected Card measure is to pH value 2 by the transudate acid treatment of concentration.

In rubbish transudate (B) or in the transudate concentrated or in purified humus sample HS4, all do not have Find Salmonella (Salmonella).

Embodiment 5)

Under agitation by 37.45 weight % hydrochloric acid of 1ml defoamer (0 weight %Dinapan 16WD) and increment (density: 1.186g/ml) adding 200ml industry to concentrate in transudate, this transudate derives from and embodiment 3-4) identical rubbish (B), but it is in different periods, there is features below:

Table 8 shows the volume and weight (ml and g) of the hydrochloric acid relative to pH value.

As with the preceding embodiment, dark-brown fluffy solid be deposited in pH value: start when 4.3 to occur, and PH value: terminate when 2.0.The 37.45 weight % hydrochloric acid (density: 1.186g/ml) of 15.6ml, the pure acid of 6.85g, correspond to altogether The transudate (sample 5pc) that 3.42g acid/100ml concentrates, it is equivalent to the acid (HCl) of 95mgmol.

After adding flocculating agent centrifugation subsequently, as in the previous embodiments, separate thick moist humus Solid (sample HS5g) 20.0g, (5pc) equal to 10%, and there is the dry residue of 25 weight % at 105 DEG C.

After 105 DEG C are dried to constant weight, in the way of identical with described in embodiment 4, the HS5g use water of a part (is used Hydrochloric acid is acidified to pH value and is about 1) carry out four continuous wash.The moist humus solid (sample HS5) of reclaiming clean, its 105 DEG C of dry residues with 36 weight %.When 105 DEG C are dry, the weight of sample HS5 equal to it available from 105 The 26% of DEG C dry HS5g weight.

Table 9 shows the characteristic of sample HS5g and HS5.

As seen from Table 9, precipitating by hydrochloric acid being used for humus, significantly reducing in purified humus insoluble Calcium sulfate and the existence of other possible inorganic compound.Thus, sample HS5 600 DEG C have 3.7% dry residual Thing (equal at the dry residue of 105 DEG C 10%), and rich in calcium sulfate sample HS4 600 DEG C have 17.3% dry residual Thing (is equal to the dry residue at 105 DEG C 48%).

Additionally, such as embodiment 1), 2), 3) shown in, this embodiment have also demonstrated for different transudate types and not Same mineral acid, occurs when being deposited in pH value less than 5 and terminates when pH value is less than 2.5.

Sample HS5g and HS5 (stove is dried 2 hours to constant weight in the air of 105 DEG C) of fraction is mixed with potassium bromide With formation tablet, in the way of identical with the HS4 of embodiment 4, obtain FT-IR spectrum thereon.HS5g and HS5 spectrum is the most non- Similar, this shows not exist significantly change after cleaning process.Both of which is good with the spectrum of commercially available prod to be superposed.

The spectrum of sample HS5g and HS5 also shows the additivity good with the spectrum of described reference material.

Embodiment 6)

By the method described in embodiment above, by former for the transudate of the Italian rubbish (C) of the ripening of 20.0kg Sample (sample 6p) is concentrated into 1/18th in the lab, to obtain the transudate (sample 6pc) of the concentration of 1.10kg, and has There is the characteristic that table 10 provides, wherein for concentrate (6pc), be important to be mentioned that the clean fall of ammoniacal nitrogen and sulfide Low.

By with embodiment 4) identical in the way of 37.45 weight % sulphuric acid are added in the transudate (6pc) of this concentration and reach To pH value 2.0, to obtain dark-brown flocky precipitate, when being separated with supernatant (settled solution of mother solution) by centrifugation Time, this precipitate defines thick moist humus sample, and it is not over water washing cleaning；Potassium hydroxide (KOH) is added to Until reaching neutral (pH value 7.0), to obtain solubility potassium humate aqueous solution (sample in this humus suspension sample HS6).Table 11 show described sample compared to the commercially available prod of potassium humate solution (COM1) and from leonardite extract another The characteristic of one commercially available humus powdered product (COM2).

It is concrete it will be seen that the sample (HS6) in solution contains in the commercial samples (COM1) being similar in solution Humic carbon amounts, and soluble inorganic salt amount (residues at 600 DEG C) is similar, consists of the alkali of chloride, sulfate Slaine (potassium, sodium), particularly powder sample (COM2) show high phosphate amount, and heavy metal is low, and at three kinds of samples It is that essence is similar between product, and is in the regulation limit of agricultural application；Obtained by extracting from leonardite Two kinds of commercial samples show high iron, but it is used as the soil improver of agricultural.

Thus, it was verified that the product forming the composition being similar in agricultural different commercially available prod used can be by leading to Cross the humus that Acid precipitation is obtained from the transudate concentrated to prepare.

Embodiment 7)

According to method indicated herein below, by the preceding embodiment 6 of humus solution form) sample (HS6) and (COM1) by Agrarian Biotechnology Department of the University of Padua, (meaning is big Profit) Chemical-Agrarian Analysis Laboratory be analyzed, measure they biological analeptic live Property:

-Fertilias Agrorum 1 (1): 47-53-Serenella Nardi, Andrea Ertani, Giuseppe Concheri, Diego Pizzeghiello-" Metodi di determinazione dell ' attivit à Biostimolante " (method measuring biological stimulant activity)

Table 12 shows properties of humus, it may be assumed that density, total organic carbon (TOC), always can extract carbon (TEC), humic acid (HA), Fulvinic acid(a necic acid) (HF)；Humification degree HD=(HA+HF)/TEC；Humic rate HR=(HA+HF)/TOC；Humification index HI=[TEC-(HA+HF)]/(HA+HF).

These two kinds of samples show similar value, all have gratifying humification (HD, HR, HI), it is typical that " ripe Change " product.

The molecular weight distribution measured by gel infiltration (LPLC) of table 13 is similar for these two kinds of samples, and And sample HS6 shows the more substantial 1st and third portion, the most relevant with humus amount of cure and biological activity.Table 14 The biological stimulant activity that measured by biological test " AUDUS " (wherein by the 3-indolyl acetic acid of these two kinds of sample increments and Gibberellin (GA3) process measure free radical formed for the suppression of Nasturtium officinale (watercress) and plumular axis extend for The stimulation of White Trieste Herba Cichorii) for sample HS6, obtain maximum auxin activity, and do not have sample to show Go out any gibberellins activity.

Finally, table 15 shows the evaluation of the biological stimulant activity on the maize seedling of 14 days；

This test (is cultivated consisting of the water of the maize seedling of 12 days is ploughed, and is replaced nutrient solution every day, be followed by 48 Hour time, wherein two kinds of humic extract samples contacts of maize seedling and two kinds of concentration (1.0ml and 0.5ml/L)) display Sample HS6 creates the growth of more preferable and good maize seedling new weight.

Therefore, the raw humus that the method even through the present invention that this example shows obtains, even without cleaning In the case of reducing soluble-salt (purification), also show the good characteristic for the application of agricultural soil modifier.

Table 1-former state (sample 1p) and the transudate characteristic (Bellolampo, Sicily) of concentrate (sample 1pc)

-embodiment 1-

Table 2-is from transudate former state (A) (sample HS1) and the characteristic of the humus of concentrate (sample HS1c)

-embodiment 1-

Humus-37.45 weight % sulfuric acid amount (density: the 1.28Kg/dm that table 3-precipitates from transudate (A)³), refer to 100mL transudate former state-mL H₂SO₄Vs pH value)

-sample 1p: transudate former state (100mL)

-sample 1pc: be concentrated into the transudate (100mL) of 1/11st

-embodiment 1-

Moist material-75 weight % phosphoric acid amount (density: the 1.57Kg/dm that table 4-precipitates from the transudate (A) concentrated³), Refer to 100mL transudate former state-(mL H₃PO₄Vs pH value)

-sample 2pc: be concentrated into the transudate of 1/12.1st, 100mL

-embodiment 2-

Moist material-37.45 weight % sulfuric acid amount that the transudate (B) that table 5-concentrates from industry precipitates (density: 1.28Kg/dm³), refer to transudate-(mL H that 100mL concentrates₂SO₄Vs pH value)

-sample 3pc.

-embodiment 3-

Table 6-humus purify (sample HS3)-with water (being acidified to pH value with sulphuric acid is 1) cleaning-

-embodiment 3-

Table 7-is from the transudate (B) (sample HS4) concentrated and the purified humus dry of transudate former state (B) Chemical characteristic

-embodiment 4-

Table 7/1-from concentrate transudate (B) (sample HS4) purified humus present in organic and inorganic Pollutant, main regulations reference

-embodiment 4-

(1) acenaphthene, phenanthrene, fluorenes, fluoranthene, pyrene, benzo (a) pyrene, benzo (b) fluoranthene, benzo (j) fluoranthene, benzo (k) fluoranthene, benzene And (ghi), indeno (1,2,3-cd) pyrene

(2) program communication block mask agent: #28, #52, #101, #118, #138, #153, #180

(3) summation at least below: gamma hch, 5a,6,9,9a-hexahydro-6,9-methano-2,4, trichloro ethylene, tetrachloroethylene, chlorobenzene

Table 8-is from precipitation HS-hydrochloric acid content 37.45%w/w (density: the 1.186Kg/ of industrial transudate (B) concentrated dm³), refer to transudate-(the mL HCl vs pH value) of the concentration of 100mL

-5pc sample

-embodiment 5-

Table 9-is before and after with acid-scrubbing cleaning, with the physicochemical property of the HS that the HCl transudate (B) concentrated precipitates

-sample HS5g and HS5

-embodiment 5-

The chemical characteristic of (the sample 6pc) of table 10-transudate (C) former state (sample 6p) and concentration

-embodiment 6-

The table 11-(HS6) chemical characteristic compared with commercially available prod (COM1) and (COM2)

-embodiment 6-

The table 12-(HS6) chemical characteristic compared with commercially available prod (COM1)

-embodiment 7-

HD=humification degree=(HA+HF)/TEC

This is a quasi-quantitative parameter: in soil and mud coal, it assumes that intermediate value (70-80), even if the most very High；In moist material (leonardite and humic extract), it has the value close to 100；Material in only slightly ripening In material (uncooked compost and organic fertilizer), it assumes that close to the value of 0；

HR=humic rate=(HA+HF)/TOC

This is a quantitative parameter: the most effective with HD same consideration；

HI=humification index=NH/ (HA+HF), wherein NH=TEC-(HA+HF)

This value is the lowest, and the amount of Soil Humus is the biggest: in moist mud coal and ripening fertilizer, it assumes that value < 0.5；In leonardite and derivative humic extract, its value is close to 1；Non-humidity material (non-ripening compost and Mud, organic fertilizer) in, it assumes that value > 1.

Table 13-analyzes the apparent molecular weight of (HS6), compared with commercially available prod (COM1)

-embodiment 7-

Result is explained

Document based on this theme considers part 1 (molecular weight > 100KD) and third portion (molecular weight > 250KD) Percentage ratio richness (abundance), it is with humus curing degree and they biological activitys that can apply are directly related.

For this viewpoint, humic extract HS6 has more preferable district compared to humic extract C OM1, three parts Point, this shows that it demonstrates the 1st and third portion of more existence and the part 2 of less existence.

Table 14-measures the biological stimulant activity of (HS6) by " AUDUS " biological detection, with commercially available prod (COM1) Compare

-embodiment 7-

Result is explained

By biological detection, this humic extract sample is compared with 3 heteroauxings and the gibberellin (GA3) of increment, come Measure free radical respectively and form the suppression for Nasturtium officinale and the plumular axis extension stimulation for WhiteTrieste Herba Cichorii.

Maximum auxin activity is found in the sample of referred to as HS6.The sample tested does not shows gibberellins activity.

Table 15-mensuration (HS6), for the biological stimulant activity of corn plant, compares with commercially available prod (COM1)

-embodiment 7-

Result is explained

The hydroponics of the maize seedling consisting of 12 days of this test, and replace nutrient solution every day, it is followed by 48 Hour time, wherein maize seedling and two kinds of concentration (1.0ml and 0.5ml/L) different humic extract samples contact.This survey Surely show for two kinds of test concentrations, humic extract sample HS6 create the overall new weight of maize seedling increase (about+ 15%), and there is the most significantly increase (+19%) under ground portion.On the contrary, sample COM1 shows average negative sense trend.

Claims (9)

1. one kind during the maturation stage that pH value is 7.0-10.0, from the transudate deriving from urban solid garbage field reclaim The method of humus, it is characterised in that:

-at the temperature of 50-130 DEG C and the pressure of 5-200kPa, make this transudate through the evaporation-concentration stage,

-make the concentration transudate acidified stage containing this humus in the solution with mineral acid, reach pH value 1-3, with Obtain the humus precipitation of fluffy solid form,

-separate to obtain raw humus from liquid phase by cotton-shaped humus solid,

Wherein by with being optionally acidified to pH value, < the water cleaning of 7 carries out the purified treatment of this raw humus, to reduce inorganic salt With the concentration of any Water-soluble Organic Substances, thus obtain purified humus.

Method the most according to claim 1, it is characterised in that being evaporated-enriching stage before, carry out transudate mistake The filter stage is to obtain the suspended sediment concentration less than 500mg/l.

Method the most according to claim 1, it is characterised in that this souring stage is carried out by adding sulphuric acid.

Method the most according to claim 1, it is characterised in that this souring stage is carried out by adding phosphoric acid.

5. according to the method described in any one in claim 1-4, it is characterised in that add alkaline hydrated oxide to this thick In humus or this purified humus, until obtaining the humus of soluble alkali salt form in the solution.

6. according to the method described in any one in claim 1-4, it is characterised in that such as get off to enter by purified humus One step purify: with selected from activated carbon, clay, kaolinic adsorbent solids process, adsorb selected from alkyl phthalates, Alkyl phenol, bisphenol-A, the organic substance of alkylbenzene sulfuric ester.

7. according to the method described in any one in claim 1-4, it is characterised in that make purified humus through being dried Process to obtain the product of powder type.

8. according to the method described in any one in claim 1-4, it is characterised in that calcium hydroxide and/or magnesium hydroxide are added It is added in purified humus, to obtain the precipitation of calcium humate and/or Humic acid Magnesium, subsequently this precipitation is sent to dry.

9. according to the method described in any one in claim 1-4, it is characterised in that stripping ammonia and volatile compound Afterwards, the condensed water obtained in the evaporation-concentration stage is used for the cleaning in the sour cleaning processing procedure of raw humus In stage.