JPS647819B2 - - Google Patents

Description

Detailed Description of the Invention The present invention uses petroleum bituminous material as a raw material to produce a granular ion exchanger with little elution of humic substances and high mechanical strength. Furthermore, by coating the surface of the grains with a mixed powder of petroleum bitumen and coal with a high proportion of coal, the inherent softening and melting properties of petroleum bitumen are improved and a special infusibility is achieved. This invention relates to a method of obtaining a granular ion exchanger by air oxidizing a granulated material as it is without any treatment.
The ion exchanger referred to here is an ion exchanger having weakly acidic cation exchange ability.

When producing granular ion exchangers from petroleum bitumen by air oxidation, the inherent softening and melting properties of petroleum bitumen must be modified in some way. Otherwise, melting and fusion will occur before reaching the temperature at which air oxidation begins, making it impossible to maintain the granular shape, or even if the granular shape is maintained, the powder will coalesce into a liquid due to melting within the granules, resulting in Oxidation occurs only on the surface.

To deal with this, a) raise the softening point of the raw material to 250°C or higher. b) After granulation, ozone,
Using a gas that has oxidizing power even at relatively low temperatures, such as NO ₂ , it oxidizes below the melting temperature to raise the softening point. c) It may be possible to use a special firing method.

However, all of these methods require complicated operations such as the use of special chemicals or the need for advanced pretreatment, and are not economically satisfactory.

As a result of intensive research aimed at improving these points, the present inventors discovered that by mixing coal with petroleum bitumen, air oxidation treatment can be performed without using special chemicals or special calcination methods. The invention has been completed.

That is, the inside of the granules is mainly composed of petroleum bituminous substances, and if necessary, coal is added in an amount sufficient to prevent coalescence due to internal melting. On the other hand, the outer surface of the granules is coated with coal to prevent fusion between the granules. This makes it possible to utilize the excellent ion exchange properties due to oxidation of petroleum bitumen.

The petroleum bituminous material that can be used as a raw material in the present invention has a softening point of 130 to 210°C, a penetration value of 1 or less, and a saturated content of 5% by weight.
It is necessary to have the following properties, and the precipitated bitumen obtained by solvent extraction of petroleum vacuum distillation residue oil or petroleum asphalt or
It is preferable to carry out air blowing treatment at 200-300°C or heat-treat the precipitated bitumen at a temperature of 200-500°C.

Furthermore, natural gilsonite, pyrolyzed pitch, etc., which have properties corresponding to these, can also be used. If the softening point is low, even if the method of the present invention is used, fusion will occur in the air oxidation process, which is not preferable.

The coal used here is preferably brown coal or bituminous coal with a hydrogen/carbon atomic ratio of 0.6 or more, and these are used alone or in combination. Coals with a hydrogen/carbon atomic ratio of less than 0.6 are not preferred because they reduce the ion exchange capacity of the product ion exchanger.

In order to satisfy the present invention, after granulating petroleum bituminous material or petroleum bituminous powder to which coal is added, the surface of the granules is coated with coal or coal powder to which petroleum bituminous material is added. It is essential to increase the content of coal. As for the granulation method, any method that allows coating after granulation can be adopted, such as granulation using extrusion molding, sizing and coating using a sizing machine, or two-stage dish-shaped granulation. There are many possible methods.

Further, as the mixed powder constituting the inside of the grain, a mixed powder containing 60 to 100% by weight of petroleum bitumen and 40 to 0% by weight of coal can be used. For the petroleum bitumen used in the present invention, an optimum mixing ratio for maximizing the ion exchange properties by oxidation of the petroleum bitumen can be obtained within the above mixing ratio range. If the mixing ratio of coal is increased more than this, the mechanical strength of the product will decrease, which is not preferable.

Water and a binder are added to this mixed powder, and after kneading and granulation, 100 to 70% by weight of coal, 0 to 30% of petroleum bituminous
The surface of the grains is coated with the mixed powder of % by weight. At this time, it is preferable to coat the core grains at a ratio of 10 to 40% by weight.

The granulated product thus granulated is then placed in a commonly used rotary kiln and air oxidized at 250-450°C.

The ion exchange capacity of the ion exchanger produced by granulation and oxidation is determined as follows. That is, accurately weigh approximately 1 g of the washed and dried sample, place it in a flask with a stopper, add 50 c.c. of 1N-NaOH, and shake well. After that, let it stand at room temperature for 24 hours, stirring occasionally, and then filter it. Take some of the liquid
Perform neutralization titration with 0.1N-HC1 and calculate the ion exchange capacity using the following formula.

C=0.1×f×(V ₁ - V ₂ )/W×50/V C: Ion exchange capacity (meg/g) W: Sample weight (g) V: Volume of liquid collected (cc) f: 0.1N- HCl factor V ₁ : 0.1N required to titrate 1N-NaOHVcc
-Amount of HCl (cc) V ₂ : Amount of 0.1N-HCl (cc) required for titrating filtrate Vcc The present invention will be explained in detail below with reference to Examples.

Example 1 A vacuum distillation residue oil was extracted with a solvent using propane, and the precipitated bituminous material was further air-blown at 260°C to obtain a softening point of 150°C, penetration of 1, and saturation content of 2.7.
% by weight of bituminous material was crushed to 200 mesh or less using a crusher.

On the other hand, subbituminous coal with a hydrogen/carbon atomic ratio of 0.92 was pulverized to 200 mesh or less using a pulverizer.

20 parts by weight of the coal powder was added to 80 parts by weight of the bituminous powder, mixed thoroughly with water and a binder, and then granulated using an extrusion granulator. The particles were further added to the coal powder and passed through a sizing machine to shape them into spheres with a particle size of 1 mm. The weight increase due to powdering was 30% by weight. This granular material was heated to 300°C at a heating rate of 50°C/hour in an air atmosphere and heat-treated at 300°C for 1 hour.
The obtained granular ion exchanger has an ion exchange capacity
The crushing load was 4.5 meq/g and 1.0 kg.

Example 2 A precipitated bitumen with a softening point of 173°C, a penetration of 1, and a saturation content of 1.0 wt% obtained by solvent extraction of vacuum distillation residue oil using pentane was pulverized to 200 mesh or less using a pulverizer. On the other hand, subbituminous coal with a hydrogen/carbon atomic ratio of 0.92
Grinded to less than 200mesh.

70 parts by weight of the bituminous powder and 30 parts by weight of the sub-bituminous coal powder were mixed well, water and a binder were added thereto, kneaded, and granulated using an extrusion granulator. The mixture was dusted with a powder mixture of 10 parts by weight of the bituminous powder and 90 parts by weight of the sub-bituminous coal powder, and then passed through a sizing machine to shape the powder into a sphere with a diameter of 1 mm. The weight increase due to powdering was 30% by weight. The granules were heated to 300°C at a heating rate of 50°C/hour in an air atmosphere.
℃ and heat treated at 300℃ for 1 hour.

The obtained granular ion exchanger has an ion exchange capacity
The crushing load was 4.5meq/g and 1.1Kg.

Comparative Example 1 Using the same raw material powder as in Example 2, bitumen/coal was mixed at a weight ratio of 6/4, water and a binder were added, and the mixture was granulated. The grains were sized while adding mixed powder of the same weight ratio. This granular material was calcined in the same manner as in Example 2, but it was fused and no granular ion exchanger was obtained.

Comparative Example 2 Using the same raw material powder as in Example 2, bituminous material/coal was mixed at a weight ratio of 6/4, and then water and a binder were added and granulated. The particles were sized and coated while adding mixed powder of bitumen/coal in a weight ratio of 4/6. This granular material was calcined in the same manner as in Example 2, but it was fused and no granular ion exchanger was obtained.

Comparative Example 3 Using the same bituminous powder as in Example 2, and using fluid coke powder with a hydrogen/carbon atomic ratio of 0.55 instead of sub-bituminous coal powder, granulation, sizing, and firing were carried out in the same manner as in Example 2. The crushing load of the obtained granular ion exchanger is
Although the weight was 1.0Kg, the ion exchange capacity was only 2.0meq/g.

Claims (1)

[Claims] 1 After granulating petroleum bitumen, air oxidation is performed to produce a granular ion exchanger with a softening point of 130 to 210.
℃, penetration of 1 or less, petroleum bitumen with a saturated content of 5% by weight or less, and 0 coals with a hydrogen/carbon atomic ratio of 0.6 or more.
A granular ion characterized by performing two-stage granulation in which a powder raw material containing ~40% by weight is granulated and then further coated with a mixed powder of the petroleum bitumen/coal in a weight ratio of 0/100 to 30/70. Method of manufacturing an exchanger.