JPH0332703A - Continuous adsorption, desorption and regeneration device - Google Patents

Abstract

PURPOSE:To efficiently adsorb a desired component by passing a mother liquor through a U-shaped vessel, moving an adsorbent contained in a basket in the vessel by a chain and adsorbing the desired component. CONSTITUTION:The materials such as nitrogen compds. and dyestuffs contained in a liq. such as mineral oil and capable of being selectively adsorbed by an adsorbent (e.g. porous silica and alumina-based ceramic) are separated and recovered from the mother liquor. In this case, the mother liquor is passed through the U-shaped vessel 11. The adsorbent contained in the basket 3 is moved in the vessel by the chain 1 to adsorb the desired component. Namely, when the desired component is nitrogen compds., the nitrogen content of the crude oil is reduced and further the content of the basic nitrogen compd. poisoning cartalyst is reduced, and the oil can be treated as such in an ordinary oil refinery. Since the adsorbent is hardly mechanically broken in the device, the high-performance adsorbent low in strength is continuously used over a long period. The separated nitrogen compds. are subjected to a chemical treatment such as dealkylation and converted to a useful material.

Description

[Detailed Description of the Invention] (Field of Industrial Application) The present invention is applicable to a wide range of adsorption operations, such as the separation and recovery of nitrogen compounds from various mineral oils containing a large amount of nitrogen compounds, such as shale oil, and the removal of specific components from wastewater. There is a possibility that it will be used.

(Prior Art) Conventionally, continuous adsorption devices for liquids include the moving bed Ha (CAP system) in the sugar refining industry and the Higgins method in ion exchange resins.

(Question H to be solved by the invention) Generally, oil obtained by carbonizing oil shale has 1 to 2
Contains vt% nitrogen. If the nitrogen content is high, the fraction obtained by fractional distillation is likely to be colored, and gum and sludge are likely to be generated. If Sierre oil, which contains an order of magnitude more nitrogen than crude oil, is processed directly at a conventional refinery, it will poison the catalyst, so the nitrogen content must be removed beforehand. Conventionally, for this purpose, a method has been used in which hydrorefining is performed in the presence of a catalyst to decompose and remove nitrogen compounds. I8! Nitrogen reactions are slow and consume a large amount of hydrogen. Therefore, if nitrogen compounds can be separated by other methods and recovered without decomposition, it would be meaningful to use them as chemical raw materials.

(!!Means for solving the problem) In order to extract only the target nitrogen compounds from the raw material, adsorption is advantageous, considering that the treated oil will be sent to an oil refinery for treatment. Moving bed equipment used in the sugar refining industry uses powdered activated carbon of IO to 30 mesh, but with relatively high viscosity sierre oil, it is difficult to remove the powder if it gets mixed in, and it has a negative impact on the subsequent oil refining process. However, the use of pumps, valves, etc. for solids transport is also undesirable because it generates fine particles.Although powder adsorbents are advantageous in terms of contact area, they are difficult for the reasons mentioned above.

Therefore, it is desirable to make the adsorbent as porous as possible to improve the contact area and increase the particle size to several millimeters. For these reasons, we have devised a moving bed system in which the weight of the adsorbent is supported by a cage. In this method, there is no place where a large force is applied to the adsorbent itself, and there is only a slight impact as it moves to the next step.

The process consists of an adsorption cylinder, a desorption cylinder, and a regeneration cylinder, which have the same basic structure, and it is efficient to bring the liquid and adsorbent into contact in countercurrent flow for both adsorption and desorption.

(Operation) Figure 1 shows a schematic diagram of the suction tube and Yue@stomach. There are gears (2) above and below the U-shaped original F4 liquid tank (1), and a chain belt (1) slowly rotates between them. The cages (3) shown in FIG. 2 are attached to the chain belt at appropriate intervals, and the cages containing the adsorbent move within the raw material liquid.

At the bottom of the basket, there is a mesh 03) with a more striped mesh than the size of the adsorbent, and when the basket is inverted, a mesh or a board is placed over it. At the top of the basket there is a horizontal gap (12) where the mandrel (14)
) so that the mandrel can move from side to side, and the mandrel is fixed to the chain. f1! The adsorbent used is preferably spherical with a particle size of several millimeters, and porous silica-alumina ceramics or the like can be used to adsorb nitrogen compounds.

The regenerated adsorbent is filled into the cage through the adsorbent supply pipe (8). The adsorbent supply pipe is electrically driven to extend at appropriate times so as not to interfere with the basket coming down from above, and to contract after filling.

The basket is placed on its side at the top of the upper gear, and the adsorbent is transferred to the next desorption process through the adsorbent recovery pipe (6), which is extended by electric drive at the same time. I was sent. The empty basket lies on the side of the upper gear, but at an appropriate time it comes out with an electric drive.90
It returns to the vertical position using the rotation knob (4). Note that it is a good idea to put a soft backing on the side of the basket to ensure that the liquid passes through the adsorbent layer.

(Example) In order to separate nitrogen compounds from oil, as shown in Figure 3, an adsorption cylinder (F) with a similar basic structure is used.Desorption 1M
(E) and U Regeneration II (D) are combined. An example is shown in which a silica-alumina adsorbent is used.
1 kg of feedstock oil (L) with nitrogen content Ik 1.5vt%
/h, As a result of feeding the adsorbent at 0.73kg/h,
Oil (K) after treatment is 0.75 kg/h (nitrogen content 0
．． 85 wt%) was obtained. Dissolve methanol as a solvent (
The oil (1) obtained by treating adsorbent <C> as J) and removing the solvent from the product was 0.21 kg/h (nitrogen content 3.3 νt%), with a small amount of nitrogen compounds. Since the adsorbent was incorporated into the adsorbent and was difficult to completely desorb, the adsorbent used was placed in a regeneration cylinder (D) and regenerated by blowing heated gas (G) at a temperature of 300 to 400° C. from below.

(Effect of the invention) As is clear from the examples, the amount of nitrogen in the feedstock oil increased,
Furthermore, since the amount of basic nitrogen compounds that poison the catalyst is reduced, it is thought that it can be processed as is in conventional refineries. In this device, the adsorbent is not easily destroyed mechanically, so weak, high-performance adsorbents can be used continuously for long periods of time. The separated nitrogen compounds are converted into useful substances through chemical treatments such as dealkylation, and are effectively utilized.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of an adsorption cylinder and a desorption cylinder used in the present invention. l: chain belt, 2: gear 3=
Cart for moving adsorbent, 4: Knob for rotating 90 degrees, 5: Gutter for collecting adsorbent, 6: Adsorbed or desorbed adsorbent,
7: Regenerated or adsorbed adsorbent, 8: Adsorbent supply pipe, 9
: Processed raw material liquid or solvent containing desorption components, 102 Raw material liquid or solvent for desorption, 11: Raw material liquid tank or solvent tank. Fig. 2 shows a basket for moving adsorbent used in the adsorption cylinder, desorption cylinder, and regeneration cylinder, 12: Gap for moving the mandrel, 13
: Wire mesh, 14: Mandrel. ′! Diagram s3 shows how to connect equipment for separating nitrogen compounds from oil, etc. A: Regenerated adsorbent, B: Adsorbed adsorbent, C: Adsorbed adsorbent, D: Regeneration cylinder, E: Deat cylinder ,
F: Adsorption tube, G: Heating gas, H: Cooling gas, ■: Solvent containing desorption component, J: Desorption solvent, K: Treated oil, L: Raw material oil. Figure Figure Figure

Claims (1)

[Claims] 1) When separating and recovering substances that are selectively adsorbed to an adsorbent, such as nitrogen compounds and pigments contained in a liquid substance, from the mother liquor, the mother liquor is poured into a U-shaped container, A continuous adsorption method in which the adsorbent placed in a basket is moved by a chain while adsorbing the target component. 2) A desorption method in which the target component is desorbed from the adsorbent adsorbed from the adsorption column while a solvent is flowing through the same type of equipment. 3) A method of regenerating the adsorbent by feeding heating gas and cooling gas from below while moving the used adsorbent from the desorption cylinder through the U-shaped regeneration cylinder using the same movement method as the adsorption cylinder.