CS271338B2 - Method of wastes neutralization that contain oil or oil derivatives - Google Patents

Abstract

The method of disposal of waste products that contain petroleum oil or, respectively, derivates of petroleum oil by active storing on dumping sites by the aid of town refuse is characterized by the fact that town refuse with a specific weight of 300 to 500 kg x m<-3> that contains at least 200 g to 400 g of organic substances in 1 kg is mixed with the weight ratio from 3:1 to 19:1 with waste products containing petroleum oil or by-products of the oil refining. Thereby, the content of petroleum oil or, respectively, derivates of the petroleum oil is modified to a maximum 5 percent of weight. The acquired mixture is deposited in storage tanks on the dumping site covered with earth that is normally used for the storage of town refuse and, additionally, the arising biogas can be gained.

Description

The invention also relates to a process for the disposal of petroleum-containing wastes or oil-containing wastes. crude oil derivatives by active storage in landfills together with 8 solid urban garbage.

Environmentally hazardous wastes include wastes containing oil or oil derivatives as the most problematic. From wastes of various states and with different contents of oil respectively. Only a few tens of thousands of cubic meters of oil derivatives are captured and professionally disposed of. deposit in public landfills. The remainder enters the environment uncontrollably and poses a permanent risk to free watercourses, groundwater and agriculturally utilized areas.

Particular difficulties are associated with the elimination of environmental pollution resulting from accidents (for example, damage to an oil pipeline, oil spills, etc.) at sea or on land, as these involve the disposal of large quantities of oil-containing substances - mostly oil-contaminated land. or perlite contained ₄ exceeding spilled oil.

for disposal of wastes containing oil resp. Petroleum derivatives are known in a number of ways.

Burning Destruction It is expensive and requires relatively high investments.

Wastes containing petroleum resp. petroleum derivatives can also be disposed of by landfill storage, depending on the type of waste deposited, it may be intermediate storage or final landfill. According to environmental and water regulations, landfills are to be set up at sites with relevant hydrogeological properties and / or with appropriate technical protection against water infiltration, therefore such landfills may only be set up at certain sites and at extremely high cost.

Wastes containing petroleum resp. petroleum derivatives can also be removed by biodegradation.

According to U.S. Pat. No. 4,328,104, oil-in-water or water-in-oil emulsions containing oil or water-in-oil emulsions are treated with biological sludge from sewage treatment plants, and the oil or oil together with excess recovered sludge anaerobically decomposed in digesters.

According to British Patent Specification No. 2,112,776, high cellulose wastes (woodworking wastes, primarily sawdust and shavings) are composted together with so-called petroleum sludge (5 to 25%). Thus, in this process, oil sludge together with the other listed nutrients (animal manure, waste from the food, paper, etc. industry) has the function of a 'biological catalyst' in the (aerobic) composting of wood waste that cannot be degraded by itself. According to the patent specification, the addition of petroleum sludge can increase the efficiency of the digestion process to which woodworking waste is subjected together with the recovered sewage sludge.

The use of this method for environmental purposes hampers the seasonal nature of composting technology or the use of compost. petroleum derivatives.

In Hungarian patent no. 174,531, it is proposed to add oil or sludge to the surface soil as a humus builder to improve loose sandy soils or bound loamy soils. petroleum derivatives and maintain the aerobic state of the soil by frequent inversion>

(plow, disc harrows) until the oil is completely destroyed (about 2 to 3 years). This method is applicable only in hydrogeological resp. agro-technologically suitable areas - ie to a limited extent * requires a large acreage and a lot of energy to maintain aerobic status.

Hungarian Patent Application Publication No. 1174/80 discloses a method by which hydrocarbon contaminated soils are incorporated to accelerate the degradation of culture contaminants consisting of groups of microorganisms capable of degrading hydrocarbons. Cellular hMCS 271338 82 tons are propagated in the soil aerobically, with the hydrocarbons serving as a source of energy, and the soil becomes again suitable for the cultivation of crops. · Similar principles are based on the Hungarian patent specifications 181,560 and 181,818, degradation of the hydrocarbons contained in the soil creates various microcultures, so-called starter cultures, which then multiply under aerobic conditions in the soil.

These methods are suitable for removing the top 5 to 10 cm of soil or oil. their disadvantages are the complexity of the preparation and maintenance of cloned microcultures and the low rate of degradation (soil without oil or oil products up to 2-3 years). These procedures are primarily suitable for the reclamation of soils and technological areas (eg oil fields, fuel transfer stations), surface contaminated by run-off oil or leaked in disaster ·

Thus, these processes offer only partial solutions for the disposal of the extremely large amounts of waste produced containing oil or petroleum products due to their low capacity and low economy.

It is an object of the present invention to provide a process by which large quantities of petroleum or petroleum-containing waste can be continuously treated by rapidly and efficiently microbiologically degrading the oil or oil derivatives. petroleum derivatives and which can be realized at a low cost without separately for this purpose; created vaccine material and without the use of supplemental nutrients ·

The invention is based on the discovery that, in the common storage of petroleum-containing wastes, respectively. petroleum derivatives and solid household garbage with oil content respectively. As a result of the special and favorable physical, biochemical and microbiological properties of this mixture, it degrades this blend to biogas in a similar way as in the decomposition of urban refuse and, as expected, under the same mechanism.

This can be inferred from the following context:

1) Solid urban garbage has a high ability to adsorb oil and / or oil. petroleum derivatives. When the content of these substances in the mixture is adjusted to about 50 g.kg ^-1 , the oil or oil is bound. petroleum derivatives gradually emerging from the waste containing such adsorption force on the surface of urban refuse such that the rate of desorption is less than the rate of degradation.

(2) The content of micro-organisms capable of degrading hydrocarbons in the oil- or waste-containing waste; Petroleum derivatives from different technologies are different but high (approximately 10 ^{3 * * * * *} to 10 ¹⁰ germs per gram).

In the microflora of urban waste (10θ to 10 ¹⁰ germs in 1 gram) there are a large number of microbes capable of degrading oil respectively. petroleum products (bacteria like Pseudomons, Flavobacterium and Astehrobacter, yeast like Candida, fungi like Aspergillus, Fusarium, penicillium). Due to the high number of germs and favorable composition of microflora in terms of degradation, taking place in several stages, the degradation of oil respectively. oil derivatives going very fast.

3) The use of solid household waste ensures the source of the nutrients of the required composition and in the quantity required for the high number of germs. Due to the extraordinary diversity resulting from the nature of the garbage, the necessary macroelements (C, N, 0, P) occur in a favorable ratio (the value of the C / N ratio is between 20 and 40), but also the energy sources (carbohydrates , lipids) and important compounds (proteins, vitamin compounds), as well as all important microelements and trace elements.

The water content of urban garbage depends on the season and the place where the garbage originates and is usually 45 to 50%. In the joint processing of urban and oil-containing waste or waste. The petroleum derivatives according to the process of the invention may have a water content close to the optimum, which is 55 to 65%.

CS 271 338 B2

4) Anaerobic degradation of oil-containing wastes oil derivatives proceed in three stages

(a) Enzymatic oxidation taking place in part under anaerobic conditions, initially involved in aerobic, later at declining oxygen concentration, optionally anaerobic, acid-producing bacteria.

aerobic bacteria r-ch ₂ -ch ₃ ------------------> R-CH ₂ -C00H ---------------- ->

facultatively anaerobic, acid-producing bacteria

R ^X -COOH + R 1 -COOH ♦ CH ₄

b) Certain anaerobic-acetogenic bacteria convert the first phase compounds into acetic acid and hydrogen.

R ^I COOH acetogenic

R ^X1 -COOH + H ₉ 0 ------------- \ CH _q -COOH + h ₂ ² bacteria ^{from J Δ}

(c) Certain anaerobic, methane-producing bacteria break down acetic acid into methane and special methane-producing bacteria (Methanococcus, Methanobacterium and Methanosorcina) are also involved in the reaction of hydrogen with carbon dioxide.

CH ₃ -COOH -------- CH ₄ + CO ₂

C0 ₂ + H ₂ -------- CH ₄ + H ₂ O in the storage of wastes containing petroleum and / or petroleum wastes. petroleum derivatives together with solid household garbage are given ambient conditions for the described degradation mechanism. after the composition of the garbage mixture into landfill, aerobic conditions prevail for about 15 to 25 days due to the physical properties of the urban garbage (loose, lump), and after the soil coverage, facultative anaerobic conditions of a later stage occur.

5) From the point of view of the development of the Unified Technology, it is an important and important finding that the degradation rate of various petroleum derivatives, such as white oil, spindle oil, machine oil and engine oil, is virtually the same as the total degradation time. Up to the initial oil content respectively. of the 70 g / kg * ¹ oil, the rate at which hydrocarbons in the waste are degraded changes only slightly.

6) As a consequence of the degradation of the favorable microbiological properties of the mixture consisting of urban solid waste and waste containing petroleum or petroleum waste. Petroleum derivatives (the rate of biodegradation is higher) can be decomposed spontaneously in landfill sites leading to the formation of biogas, thus accelerating the recovery of gas.

It is therefore an object of the present invention to provide a process for the disposal of petroleum-containing wastes or oil-containing wastes. The object of the present invention is to mix solid urban garbage with a specific weight of 300 to 500 kg / m ³ containing 200 to 400 g of organic matter in 1 kg, intensively mixed in a weight ratio of 3: 1. to 19: 1 with waste

EN 271338 02 containing petroleum or petroleum by-products, thereby adjusting the oil content and / or oil content. of the petroleum derivatives in the mixture to a maximum of 5% by weight, the resulting mixture is optionally deposited in a landfill landfill commonly used for municipal waste disposal, and optionally the biogas produced is recovered.

All petroleum-containing wastes or oil-containing wastes are suitable for the process according to the invention. petroleum derivatives containing petroleum respectively. Crude oil products not exceeding 50% by weight but containing no additives toxic to microbiological processes.

The process according to the invention can be used in urban waste landfills operated with so-called controlled storage, to which other waste is not bound.

In order to prevent possible contamination of groundwater by leaking water, it is expedient for the landfill and the mixing of waste containing petroleum and / or oil. The oil derivatives carry on the surface of a previously folded layer of urban garbage at least 5 meters thick, which was compacted to a density of 500 to 700 kg.nT ³ and then covered with a layer of soil 30 to 60 cm thick.

The invention is illustrated by the following examples.

Example 1

In a pilot plant simulation facility equipped with a leakage water returning, gas recirculation and analysis facility, the accelerated degradation of a 0.2 m ³ mixture of petroleum derivatives containing household garbage was investigated.

The oil derivative content was adjusted to 50 g in 1 kg using the garbage, the parameters of which are given in Table i. Household wastes contained 342 g of organic matter per kg and 42.7% of water, with a density of 307 kg.wT ³ .

Table 1

Waste Moisture content % Oil content g.kg ¹ Own microflora waste Number of germs v 1 g cooling and lubrication 86.9 119 Flavobacterium) 3,8.10 ⁵ emulsion sporobacteria) Staphylobotritis ) Trichoderma ) 0,5.10 ³ Mucor ) Aspergillus flavus ) oil contaminated sawdust 38.8 102 Gram-negative bact. Pseudomonas ) ) 1,2.10 ⁵ oily 8.8 148 Gram-negative bact. ) 4,2.10 ⁷ rags Pseudomonas Trichoderma Flusarium Mucor) 50 Candida 9.10 ³ waste from car washes 61.4 82 Flavobacterium (Pseudomonas) 1,1.10 ⁵ dishwasher waste 96.1 11 Flavobacterium ) cars sporotvorné bakt. ) 8.10 °

The moisture content of the mixture was 59.2%.

The simulator cell was closed after filling and the mixture contained therein was ventilated for 7 days. after interruption of ventilation, the amount and composition of the leaking gas as well as the parameters of the leaking water were continuously measured. The experiment lasted 250 days.

In the initial period the content of organic compounds in the seepage water increased to a maximum of 31 days, and this coincided with the highest oil content in the seepage water (48 mg.dm * ³ ). The formation of gas was negligible, the methane content being at most 3%.

After 50 to 70 days, gas evolution intensified, the composition of the gas constantly changing until 65% of methane and 30% of carbon dioxide were reached. This ratio was maintained for approximately 150 days. In this time period the content of organic substances in the seepage water was smaller, the highest oil concentration was around 10 mg.dm ³ .

at the end of the experiment, the simulator cell was emptied and the remaining oil content was determined. It was still 4.51 g.kg * ¹ , which results in a 91% efficiency for oil degradation. Thus, the amount of oil carried by the seepage water was at most 0.006% _t based on the original amount of oil.

In addition to the process described above to simulate landfill disposal, an attempt was made to determine the adsorption of oil. The leaking water leaving the simulator cell was led through a 2.0 m long column with a useful volume of 1.3 dm ³ , filled with urban garbage. The water flowing from the column was practically free of oil throughout the experiment (the highest oil content was 5 mg.dm ³ ). When emptying the column, it was found that the largest part of the oil was bound in the upper quarter of the column to urban waste. After 1,700 mm, it was virtually impossible to detect oil contamination.

Example 2

In the first phase, the technology which avoided oil contaminated wastes was examined, and the oil content, water content and microbiological degradability of the waste were examined.

The landfill site for this experiment was created in an area where solid urban garbage is exported by placing the sump in a separate location. The collar had a volume of at least 1,000 m ³ , meaning that its useful area corresponded to the amount of garbage collected in three months. Side walls Pits They are made of urban garbage. The height of these prismatic walls is 3 to 4 meters. The area in the crown of the sump forms the transport path for transport vehicles and working machines, and is therefore set up in a width of approximately 3 m and compacted by compacting to the appropriate strength. Sprinkled and compacted prisms enclose an area of approximately 30 m long, 10 m wide and 3 to 4 m deep. It is possible to modify the other wells by extending in the longitudinal direction according to the speed of filling the wall of the well.

On the shorter side of the sump located at the filling point, a waste mixing area of at least 8 meters in length is as wide as the sump. This waste mixing area is covered with a layer of 0.4 to 0.5 m thick soil which suffers.

Household refuse, calculated on the basis of the oil content of oil-containing wastes, which have an average specific gravity of 420 kg.m ³ and contain 250 g of organic matter per kg, creates a bed of about 6 m wide on the mixing surface 50 cm thick. Oil-containing wastes are unloaded on this bed of garbage and spread evenly over the surface with the machinery. The uniformly layered wastes are then inverted and mixed with household garbage several times with a grader or grab. The oil content of the mixture is adjusted to 3 to 5%, the moisture content to 50 to 60%. The well is then filled with the mixture.

The mixing surface is re-treated and any contaminated oil is removed by the grader. The contaminated soil is poured into the sump and the mixing surface is covered with fresh soil, the tank is filled frontally from the side of the mixing surface. Oakmile reaches the crown height, advances the mixing surface - subject to the above conditions - further down the surface of the filled part of the sump · Pipes used for the extraction of biogas are laid 1 to 3 years after filling the sump ·

Example 3

The landfill of solid urban waste, based on the described pit filling technology, treated 2,000 tons of oil-containing waste per year from automobile maintenance and engineering plants.

14,000 m ³ of household garbage in housing estates, which were pre-crushed in garbage trucks, were used for mixing, the average specific gravity of household garbage was 390 kg.m * ³ , the organic matter content was 240 g in 1 kg. The water content of the mixture was adjusted to 57 Mixtures were filled with three sumps, each with a useful volume of 5,000 m ³ .

The microbiological degradation processes of the oil were checked by analyzing samples taken from boreholes at different depths.

In the section of the sump filled already 12 months ago (borehole no. 1), the oil was decomposed already 95-97%, and also after 6 months (borehole no. 2), the decomposition was 90-93%. Well # 3 was made near the filling queue; the measured values show the initial composition of the mixture.

Table 2

borehole depth («) Oil content (9 · kg “ ¹ ) borehole · 1 borehole no. 2 vrt ¢. 3 0.0 to 1.0 2.40 5.0 29.7 1.0 to 2.0 1.84 3.25 43.5 2.0 to 3.0 1.62 3.72 4,5 3.0 to 4.0 1.72 7.62 38.2 4.0 to 5.0 1.43 4.57 4.1 5.0 to 5.5 0.02 0.09 0.04

Samples obtained from wells also confirm that the layers lying below the mixture and containing only urban garbage were virtually free of oil contamination, traces of oil could only be detected at the layer contact.

In the well No. 1, representing approximately one year of degradation, a gas sampler was placed. As shown by gas analysis results, the biogas produced contained 59% methane, 39% carbon dioxide and 2% other gases. · In a landfill site containing exclusively urban waste only gas containing 35% methane, 50% carbon dioxide and 5% other gases was produced.

Example 4

To dispose of soil contaminated by an average of 6.5% of oil in the event of a pipeline failure, this soil was mixed with three times the amount of urban waste. These municipal garbage had an average specific gravity of 480 kg / m ³ and contained 210 g of organic substances in 1 kg. The volume moisture content of the mixture was adjusted to 55%, the oil content was 2.2% ♦

The mixture was stored in a landfill technology dump site · Oak could be expected based on the initial composition, the degradation rate was less and to achieve an efficiency of 95-97% <shown in Example 3, twice the time required ·

Example 5

The oil spilled from the damaged tanker into the sea was surrounded by a floating wall on the water surface and then removed by perlite from the water surface · The resulting 400 tons of oil-polluted perlite, which had an average oil content of 16% _t, were deposited as described in Example 4 the garbage had a specific weight of 493 kg.m “ ³ and contained in 1 kg 203 g of organic substances · The oil content in the mixture for landfill was adjusted to 4.7% and the water content to 62.7% · The degradation rate was practically as high as in example 4 ·

Claims (1)

A process for the disposal of petroleum-containing wastes or petroleum derivatives using urban garbage, characterized in that solid urban garbage with a specific weight of 300 to 600 kg / m ³ containing 200 g to 400 g of organo-organic substances in 1 kg is intensified. mixed in a weight ratio of 3: 1 to 19: 1 with petroleum-containing wastes or by-products of the oil refining, and the resulting mixture is deposited, where appropriate, in landfills covered with soil ·