KR850001095B1 - Treatment process for oil-sluge - Google Patents

Abstract

In a treatment method for oilsludge in a fluid situation using additives or heat the sludge in the fluid situation is suppled to the sintering apparatus of cement. The combustible material in the oilsludge is completely burned and is used as a heat source in the sintering of cement. The incombustible solid component is crushed in a kiln and is mixed in to the cement as a cement component.

Description

Treatment method of oil sludge

The accompanying drawings show an example of a cement firing apparatus that can be implemented according to the present invention.

* Explanation of symbols for main parts of the drawings

1: feeder 2: manned fan

3: Suspension Preheater 4: Cyclone

5: year 6: Kasoto

7: heavy oil blowing device 8: rotary kilo

9 fuel injector 10 connection structure of suspending preheater and kilolon

11: clinker cooler 12: vibration suppression cyclone

) 이분(泥分) 등을 주성분으로 하는 불연성 고형물(不燃性固形物)을 시멘트 소성공정에서 유효하게 이용하는 데 있는 것이며, 또다른 목적은 위와같은 오일슬러지를 공해, 예컨데 환경오염의 문제점을 야기시킴이 없이 처리하는 방법에 관한 것이다.The present invention, as well as the heat of the oil sludge which is currently incinerated mostly, as well as iron iron contained in itself (

) It is to effectively use non-combustible solids, which are mainly composed of bismuth, etc. in cement firing process, and another purpose is to pollute the oil sludge as above, causing problems of environmental pollution. It is about how to handle without this.

The term "oil sludge" herein refers to oil sludge in ships, oil sludge in a fixed oil tank, petroleum hardwood or edible oil. It refers to all things according to the place and cause of various occurrences, such as oil sludge generated with washing, and according to the method of the present invention, its properties, the amount of non-combustible solids, and its components are not limited at all. .

) 이분(泥分) 등]을 함유하고 있으며, 3000-7000Kacl/kg 정도의 발열량을 보유하고 있다. 또 상온(常溫)에서는 몹시 끈끈한 고형물이나, 50-60℃ 정도 이상으로 가온하면 유동성이 생겨서 그 취급은 용이하게 된다. "표 1"에 원유의 저장에 수반하여 발생한 오일슬러지 및 윤활유의 정제에 수반하여 발생한 오일슬러지의 예를 하시한다.The characteristics of oil sludge vary greatly depending on the cause, place, oil type, and history of oil sludge. Generally, about 40-60% of incombustible solids [mainly iron tablets (

) And has a calorific value of 3000-7000Kacl / kg. In addition, at room temperature, when heated to a very sticky solid or about 50-60 ° C. or more, fluidity is generated and the handling thereof becomes easy. In Table 1, examples of oil sludge generated with the storage of crude oil and lubricating oil are given.

Conventionally, oil sludge is difficult to handle due to its physical properties, has many non-combustible contaminants, and in some cases, harmful ingredients (eg, sulfur, vanadium, etc.) concentrated in sludge, are effective in general industrial fields. Effective use of treatment or calories is almost impossible and most of them have been incinerated.

TABLE 1

Examples of the appearance of oil sludge

(Experimental process)

) 처리 등을 행할 필요가 있으며, 오일슬러지의 소각과 여기서 파새할 염려가 있는 공해방지에 막대한 비용과 인력을 소비하고 있음은 주지의 사실인 것이다. 또한 소각 잔회에 관하여 말할 것 같으면 특히 원유계(原油系) 슬러지는 철과 철의 산화물이 주성분이거나, 1% 정도의 유황을 함유하고 있기 때문에 제철원료로서는 그다지 바람직 하지 못한 것이며, 또한 정제계(精製系) 슬러지의 소가잔화는 점도광물에 기인하는 SiO₂및 Al₂O₃가 주성분으로서, 그 어느 소각잔회도 종래에는 매립용 등으로 폐기되었을뿐 자원활용면으로 보아서도 그 여지가 있을 것 같은 데도 불구하고 아직은 실현되지 못하고 있는 상태이다.In the incineration of oil sludge, it is generally packed into the processing plant in a packaged state, and is injected into a rotary kiln for incineration as it is, and then incinerated at a temperature of about 800 ° C. while using crude oil. In the case of disposal of parent and drainage, and in most cases, flue gas desulfurization (

It is well known that it is necessary to carry out the treatment, etc., and it consumes enormous cost and manpower for the incineration of oil sludge and the pollution prevention which may engulf here. In addition, in the case of incineration residues, in particular, crude oil-based sludge is not preferable as a raw material for steelmaking because iron and iron oxides contain about 1% sulfur. Slurry calcining of sludge is mainly composed of SiO ₂ and Al ₂ O ₃ due to viscous minerals, and all of the incineration residues are conventionally disposed for landfilling, but may be considered as resource utilization surfaces. Despite this, it is not yet realized.

As described above, the oil sludge has been incinerated only as waste products because of its recirculation point, which is not only an effective treatment in the general general industrial field but also an effective use of the calories. A new method, which has not been known so far, has been devised, which is an extremely simple, effective and pollution-free method of treating oil sludge in a cement firing process.

), 철정광(鐵精鑛) 등 철성분 함유뮬을 계량(計量) 혼합하고, 미분쇄하여 소정 과학성분으로 조정한 후, 시멘트 클린커 소성용로에서 145℃ 정도로 소성한 다음, 석고를 첨가해서 미분쇄하여 시멘트를 제조하고 있는 것이다.In the cement industry, on the other hand, as a raw material for iron, together with various raw materials such as limestone, clay, silica, serpentine,

), Iron concentrates such as iron concentrate, etc. were weighed and mixed, finely pulverized and adjusted to a predetermined scientific component, and then calcined at about 145 ° C. in a cement clinker firing furnace, and then gypsum was added. And finely pulverized to produce cement.

In the adjustment of the raw material for cement firing clinker firing, the mixing ratio of various raw materials to be used is the main constituent mineral of cement clinker according to the chemical composition of each raw material to be used and the kind of cement clinker to be used. 3CaO · SiO _2, is determined _{2Ca · SiO 2 4CaO · Al 2} O 3 · Fe 2 O 3 considering the chemical Sung required to generate the like. In the cement firing process, since the raw material of limestone is calcined in the cement kiln, the cement calciner itself is an extremely high-efficiency lime-based desulfurization apparatus, and is used for the desulfurization of flue gas. It is well known that desulfurization facilities are also unnecessary, and in the cement industry, high efficiency dust collectors, such as electric dust collectors, have been equipped from early on, and therefore, countermeasures have been taken against so-called dust pollution.

Particularly in the cement firing method in which a suspension preheater is installed, in addition to desulfurization under a suspended state in the preheater, the preheater exhaust gas is again used as a heat source in a dry grinding process. There are many and the desulfurization efficiency becomes higher as a result of re-contact with fine limestone here.

Here, the main components of the combustion sludge of the oil sludge are all contained in the main constituent minerals of the cement clinker, and the sulfur content is fixed in the clinker as a result of the contact desulfurization with fine limestone to crush the cement clinker. It partially replaces gypsum (CaSO ₄ · 2H ₂ O) which is added to adjust the setting time of product cement.

The present invention is to treat the oil sludge in the cement firing process by combining the properties of the oil sludge and the function of the cement calciner as described above. It is effectively used as a part, and the sulfur and solids are fixed and utilized in the cement cleaner mineral or as the cement cleaner component mineral, so that the oil sludge is extremely simple without installing any special pollution treatment or after treatment facilities. Is effective and harmless, and its industrial value is very large.

According to the present invention, while maintaining the oil sludge in a flow state, the oil sludge is effectively treated by supplying it to the cement firing apparatus for combustion.

Here, the fluid state refers to a state in which oil sludge can be mechanically supplied to a cement firing apparatus and can be uniformly mixed with the cement raw material. For example, a slurry phase, a liquid phase, a cake phase, and a pellet Phase, granular, powdery, gaseous, etc.

Oil sludge is extremely sticky solids at room temperature, so it is not fluid and its operation is very difficult. In the present invention, the oil sludge is heated or fluidized to facilitate the operation of the oil sludge, such as by adding an additive thereto. That is, depending on the properties of the oil sludge, for example, only heating or addition of an additive may be sufficient, or it may be advantageous to carry out by a combination of these means.

These means are particularly effective for maintaining oil sludge in a liquid phase, known as a liquid phase.

)형 교반기 등과 같은 교반기로써 교반하면서 그와 같은 조작을 행함이 바람직하다.In the case of heating the oil sludge and adding an additive, a propeller type stirrer, a turbine type stirrer, and a drawing (

It is preferable to perform such an operation, stirring with a stirrer, such as a) type | mold stirrer.

When heating the oil sludge, although it is not constant depending on the type of oil sludge, the sludge may be heated to a temperature at which the sludge can maintain a flow state, but it is generally about 40-90 ° C., ideally 60-80 ° C. Warming is in the range of.

The additives added to the oil sludge are used to lower the flow point and viscosity of the oil sludge, for example, about 5-50% by weight of fuel oil (large oil sludge). About 0.1-0.5 weight% (oil oil sludge fraction) of the conventional pour point fall material, or about 5% weight (oil oil sludge oil) of the conventional viscosity-lowering agent is added.

Depending on the origin of the oil sludge, for example, it may contain bulk solids such as iron clumps. When such oil sludge is treated as it is by means of heating and additives, There is a possibility that the blockage may occur due to the bulk solids, and it is not uniformly dispersed in the cement raw material, and thus a uniform fumiled clinker cannot be obtained. With respect to such oil sludge, when it is pulverized by a mill such as a bowl mill, the oil sludge is gradually fluidized by the heat of pulverization, and the bulk solids are pulverized in the slurry state. If it is difficult to fluidize easily due to the property of oil sludge, fluidization is promoted by adding 5-50% by weight of oil such as fuel oil and grinding /

Depending on the type of oil sludge, fluidity such as liquid phase or slurry phase may not be obtained as a means of heating or addition of additives as described above. For such oil sludge, a pug mill (Pug Mill) At one end of the admixture such as), the cement raw powder is mixed and kneaded by about 1-10 times the amount of oil sludge, and then mixed with the oil sludge at the same time and discharged to the other end.

Although the discharge is taken out of the cake phase with less adhesiveness, the properties of the discharge have been improved to some extent in the operation of transportation, supply, etc., but if necessary, the discharged product may be re-molded or assembled. As the method, well-known methods, such as extrusion molding, consolidation shaping | molding, rolling assembly, are applied.

By forming or assembling in this way, the oil sludge can be easily transported, stored, etc. like ordinary granular materials.

The amount of the cement raw material powder used for mixing and kneading the oil sludge can be appropriately added or subtracted according to the properties of the oil sludge, etc. It is also possible to use one or two mixtures of cement powder or cement clinker powder in cement raw powder. In this case, the addition of a small amount of water in addition to the water present in the oil sludge is particularly effective for the hardening of the moldings or granules, and the moldings or granules thereof can be stored in relatively large quantities.

In addition, depending on the type of oil sludge, it may be advantageous to separate and treat it as oil and solids.

The oil sludge is warmed to a temperature capable of having sufficient fluidity (60-80 ° C.), and the oil and solids are mechanically separated or thermally decomposed to separate the solids. In this case, a known method such as centrifugal separation, pressure filtration, etc. for mechanical separation, or fluid decomposition, for thermal separation may be applied.

Solid content separated from the oil is one of the raw materials for the cement raw material combination, and is supplied to the appropriate place during the cement raw material manufacturing process such as the grinding process to prepare the cement raw material together with other raw materials, or the solid part alone It may be pulverized and prepared as a cement raw material.

The method for fluidizing the oil sludge is not limited to the method described above, and other methods may be selected as long as it is a method capable of maintaining the oil sludge in the fluid state.

The method of the present invention is also applicable to cement kilns made of kilns, suspending preheaters and cement kilns made of kilns, cement kilns made of suspending preheaters and plasticizers. will be.

A known cement firing apparatus in which a suspension preheater with a gas furnace is installed is illustrated in the drawing, and the kiln includes a rotary kiln, a shaft kiln, a mobile kiln, an airflow kiln, and the like. This includes various kilns.

The place where the oil sludge fluidized by the above-described method is supplied to the cement firing apparatus is determined in consideration of the fluid state of the oil sludge, the properties and the degree of calcination of the cement raw material. For example, the oil sludge is supplied to any one or more of the kiln for cement firing, the cement raw material kiln and the suspension preheater, in which case it is introduced by the usual method so as to be uniformly mixed with the moving cement raw material. do.

As the place for supplying the oil sludge, there are typically the above-mentioned places, which can be appropriately selected depending on the fluidization state of the oil sludge supplied. An example of the suitable supply place will be described below with reference to the drawings. It is not limited to.

When the flow state at the time of supply is a liquid phase, it may supply in a spray form or may be injected in a pipe, but it is preferable to supply in a spray form especially. As a supply place, the kiln (8) suitable is a cement raw material temperature among them. Downstream along the flow of the raw material near the decomposition temperature of the stone, especially suitably clincher's mouth, cement raw material furnace (6), suspension preheater (3), suitably the highest cyclone ( cyclone) is supplied to one or more places of the cyclone 4 or flue 5 at the lower end, and the connecting structure 10 of the suspender preheater and the kiln.

When the oil sludge is supplied in the slurry form or the gas phase, it is supplied to the same place as the case where the oil sludge is supplied in the liquid phase.

In the case of granular, cake-like or palletized oil sludge, the kiln (8), preferably downstream of the raw material stream near the decomposition temperature of the dilution stone, cement raw material furnace (6), Suspension preheater 3, suitably at the uppermost cyclone, is supplied to any one or more of the lower cyclone 4 or flue 5 or the connecting structure 10 of the suspension preheater and kiln.

As described above, depending on the properties of the oil sludge, the oil and solids may be separated and processed, but in this case, the oil is supplied in a gaseous and liquid flow state, and the solids are supplied with a cement raw material by a conventional method. .

Regarding the method of the present invention, a typical series of operation examples will be described in detail as follows.

(Operation Example 1-1)

)으로 분무하기에 충분한 저점도(底粘度)의 유동상태로 유지하여, 부설된 전용의 버어너를 통하여, 예컨데 시멘트 소성용 킬른의 클린커 배출구로부터 킬른으로 분무상태로써 불어 넣는다. 이와같이 공급된 오일슬러지는 주위의 고온도(위의 불어넣는 장소의 경우, 가스온도 1,900-2,200, 재료온도 1,000-1,450)로 순식간에 연호하며, 시멘트 원료의 가소(假燒)와 소결에 이용됨과 동시에 고형분은 그 킬른속에 살포되어 킬른의 혼합 효과에 의하여 통상방법으로 공급된 시멘트 원료분말에 균일하게 공급되어 시멘트 클린커에 소결 된다. 또 오일슬러지의 중의 유황분은 킬른에 있어서는 주로 가소대(假燒帶), 서스펜선 프리히이터가 부설된 킬른에 있어서는 주로 그 프리히이터 중에서 원료분말에 흡수되어 클린커중에 고정된다.Warming the oil sludge to about 60-80, adding an additive as described above, or a combination of these means (

It is maintained in a state of low viscosity flow sufficient for spraying to a), and is blown into the kiln from the clinker outlet of the kiln for cement firing, for example, through a dedicated burner installed. The oil sludge supplied in this way is rapidly softened to the surrounding high temperature (in the case of the above blowing place, the gas temperature of 1,900-2,200 and the material temperature of 1,000-1,450), and is used for calcining and sintering cement raw materials. At the same time, the solids are sprayed in the kiln and uniformly supplied to the cement raw material powder fed by the conventional method by the mixing effect of the kiln and sintered in the cement clinker. In the kiln, the sulfur content of the oil sludge is mainly absorbed by the raw material powder in the preheater and fixed in the clinker in the kiln in which the kiln, in which the suspension preheater is placed, is mainly fixed.

The place of supply of the oil sludge is not limited to the above examples, and if the raw material temperature is downstream from the bottom of the limestone decomposition temperature (typically 800-900 ° C.), preferably in the furnace or in the middle of the kiln. Anywhere is fine. In such a place, the heat of combustion of oil sludge is used almost entirely because of the calcination of the surrounding cement raw material (decarbonation decomposition of limestone), which is advantageous in terms of thermal efficiency. In particular, in the firing apparatus in which the suspension preheater is installed, the connection structure of the preheater and the kiln or the preheater can be supplied to the cyclone or the year, if desired.

However, in the multi-stage suspension wire preheater, the temperature is lower toward the upper end, and is usually about 300-350 ° C at the upper end, so that the vaporized oil is discharged as it is without burning even when the oil sludge is pressed in such a place. Even if it burns, even if it burns, it is discharged as it is without giving sufficient contribution to heating or partial plasticization of the cement raw material due to the short contact time with the cement raw material. As a result, not only the heat of combustion of oil sludge can not be effectively used, but also the absorption of sulfur by cement raw materials is not enough.

(Operation Example 1-2)

According to another series of operations, oil sludge with bulk solids is pulverized with a grinder such as a bowl-mill by adding oil such as fuel oil as necessary. Slurry oil sludge obtained by such pretreatment is processed by the same operation as the series of operation mentioned above.

(Operation Example-3)

According to another series of operations, one or more of the cement raw powder, cement powder or cement clinker powder is added to the oil sludge and mixed and kneaded with a blender such as a pug-mill. You may shape | mold or assemble by a well-known method as mentioned. In this case, the addition of a small amount of water is effective for curing the molding or granulated product.

)로 인하여 통상의 방법에 의하여 공급된 원료와의 혼합은 더욱 완전한 것이 된다. 이와같이 오일슬러지 중의 고형분은 시멘트 원료 중에 균일하게 혼합되어 시멘트 클린커의 조성성분으로서 공급되며, 한편 오일슬러지 중의 가연분(可燃分)의 연소열은 주로 원료의 분해에 유효하게 이용된다. 가스중의 유황분은 전술한 바와 같이 클린커중에 고정된다.The cake-like material, molding, and granulated material of the oil sludge obtained in this way are common conveyers such as belt conveyors and bucket elevators. As a conventional transporting device, for example, a connection structure portion of a preheater and a kiln of a firing facility in which a suspension preheater is installed is supplied to be mixed with a raw material introduced by a conventional method. The oil sludge supplied in this way is extremely rapidly heated at ambient high temperatures (in the case of the above-mentioned supply place, the material temperature of 800-850 ° C and the gas temperature of 1,000-1,100 ° C), resulting in the release of the volatiles from the inside, The cake-like or granulated product of oil sludge is immediately differentiated, and again the effect of electric mixing in the next kiln (

), The mixing with the raw materials fed by conventional methods is more complete. In this way, the solid content in the oil sludge is uniformly mixed in the cement raw material and supplied as a composition component of the cement cleaner, while the heat of combustion of the combustible powder in the oil sludge is effectively used mainly for the decomposition of the raw material. The sulfur content in the gas is fixed in the clinker as described above.

The oil sludge supply site is not limited to the above, but can be supplied to each of the aforementioned locations except for the kiln's clinker outlet.

The supply of cake sludge or molded and assembled oil sludge to the kiln discharger of the kiln has a short residence time in the kiln, resulting in incomplete mixing with the raw material supplied by a conventional method, and the composition of the sintered clincher. This is undesirable because bias occurs.

(Operation Example-4)

According to another series of operations, the oil sludge is heated to a temperature (60-80 ° C.) capable of assisting sufficient fluidity, and the oil and the solid are separated mechanically or thermally decomposed to separate the solid from the solid. In this case, a known method such as centrifugal separation, pressure filtration, etc. for mechanical separation, and fluidization, etc. for thermal separation is applied. Mechanically separated oil can be supplied as described in "Operation Example -1", and thermally decomposed oil is mostly gaseous, and particulate decomposed coke may be mixed therein, It is possible to supply it to a place as described in "Operation Example-1" through the burner. The heat source for pyrolysis is sufficient as the oil sludge's own partial oxidation heat, and no external supply of heat is required.

On the other hand, the solid content separated from the oil is one of the raw materials for the cement raw material combination, and is supplied to a suitable place such as a crushing step in the cement raw material manufacturing process and is prepared as cement raw material together with other raw materials. In each of the above-mentioned operations, the limestone, clay, etc. of Kita are previously prepared so that the clinker finally sintered according to the amount of oil sludge used, the amount of incombustible solids in the oil sludge, and the chemical composition thereof has the desired chemical composition. Of course, the blending ratio of the raw materials is determined.

As described above, the present invention uses the oil sludge as part of the heat source for calcination of cement cleaner and at the same time contains the non-combustible solids and sulfur which generates secondary pollution by combustion. By using it as a source of waste, it is a pure waste, which entails enormous cost and manpower, and treats only the resources being incinerated in an extremely simple way.In terms of waste treatment, it is an effective and pollution-free treatment of waste. In terms of cement firing, the replacement of parts of fuel and raw materials with extremely inexpensive materials is of great industrial value.

EXAMPLE

As shown in the drawing, an example is given of a method of treating oil sludge in a process of firing a ordinary Portland cement clinker by a cement firing apparatus in which a suspending preheater with a gas furnace is installed.

80% by weight of limestone, 16% by weight of clay, 0.7% of iron raw materials, and 3.3% by weight of corners are fed and pulverized cement raw material is fed to the suspension preheater (3) by the feeder (1). The raw material is used for heavy oil by the heavy oil blowing device (7) to the calciner.

In the proportion of g, it is fired in the form of a spray and burned in the gas furnace (6), and from the clinker outlet of the rotary kiln (8) to the fuel oil (9) to 10% of heavy oil in heavy oil. The raw materials in which the corresponding crude sludge was mixed (hereinafter referred to as "mixed fuel") were blown and burned in a spray form at a rate of 54 kg per ton of clinker.

The crude sludge has the properties as shown in "Table 1", and it is very sticky at room temperature and there is no fluidity, but it is heated to 60 by a heating device and mixed with the heavy oil.

As described above, the cement raw material supplied to the suspender preheater 3 is preheated and calcined with the suspender preheater in the same process as the firing of a conventional cement clinker, which is calcined in a furnace and then again in the rotary kiln. It proceeds from the finishing calcining in the direction of sintering to reach the clinker outlet. Here, the mixed fuel blown into the spray state from the fuel blowing device 9 burns immediately and contributes to the firing of the clinker. In addition, the sulfur content contained in the mixed fuel is once burned and becomes SO ₂ , which is fixed to the limestone powder in the passage ash of the exhaust gas, especially in the suspending preheater in contact with the calcined suspended limestone powder. On the other hand, the solid content in the mixed fuel is dispersed in the front surface of the kiln by blowing as a spray state, and is dispersed up to about 30m at a given initial speed due to the combustion device and the wind speed of the supplied air. Evenly distributed. In this zone, the raw material temperature has already reached about 1, 100-1, and 200 ° C, so that the solids are immediately applied to other raw materials to form a homogeneous clinker, and the solids in the mixed fuel are shown in "Table 1". As the iron is rich, the raw material supplied to the suspension preheater (3) is prepared by reducing the amount of iron, taking into account the portion thereof. It is no different.

The components of the resulting cement clinker are as follows.

SiO ₂ 22.7%

Al ₂ O ₃ 5.4

Fe ₂ O ₃ 3.3

CaO 66.1

MgO 1.2

SO ₃ 0.7

Since the clinker contains sulfur content, by reducing the amount of gypsum added at the time of the clinker grinding by the content thereof, a cement which is not at all different from the cement by the normal firing method is obtained.

Claims (1)

In the method of treating oil sludge by maintaining the oil sludge in a fluidized state by heating or addition of additives, as shown in the drawing, when the oil sludge in the fluidized state is supplied to a cement baking apparatus, the combustible powder (oil) Is completely burned and used as a heat source for cement firing and the non-combustible solids are pulverized in the kiln and mixed into the cement constituent mineral source.

Images