JPS6021196B2 - Binder manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for continuously producing a sticky agent having properties superior to petroleum-based heavy oil.

More specifically, it provides a new manufacturing method that incorporates the circulation method and the Takaazusa method.

Japan relies on imports for most of its coking coal resources for steelmaking blast furnaces.

However, due to the recent increase in steel production and the global shortage of coking coal, there are concerns that there will be a shortage of coking coal for steelmaking blast furnaces in the future.

As a countermeasure to this problem, research and development of sticky agents has become an urgent issue. Conventionally, there is a binder for molded coke, and the caking agent used as a caking agent is coal tar pitch, but coal tar pitch is small in quantity and has recently been replaced with petroleum-based powder, which has no use other than road paving. Research and development is underway to create a binder from quality oil.

However, when producing a viscous agent by heat-treating petroleum-based military oil, petroleum-based heavy oil, unlike coal tar, tends to undergo rapid thermal decomposition or rapid thermal polymerization, resulting in coking problems. has.

Therefore, as a countermeasure for this problem, conventional methods include mixing coal into heavy petroleum oil and heat-treating it and scraping off the coke generated inside the reactor from adhering to the inner wall of the reactor using coal particles, or by blowing high-temperature steam into the reactor. A method is being used to prevent caulking using the Takaazusa effect. However, the former method requires removal of coal powder as a post-treatment, and the latter method requires the use of a large amount of expensive steam.

The present inventors have established an excellent process that uses a circulation method and a sanding method in combination with the heat treatment method to suppress rapidly occurring thermal decomposition and thermal polymerization reactions, prevent coking troubles, and continuously produce a viscous striping agent. reached.

The process of the invention consists of a mixer and a number of reactors. In the mixer, the raw petroleum-based vehicle oil and the reformed petroleum-based virgin oil taken out from the reactor are mixed.

The mixed petroleum-based soybean oil may be extracted from a single reactor, or it may be a mixed modified soybean oil extracted from several reactors, but it can often be used to obtain the characteristic values of the desired sticky mackerel agent. The implementer should take this into consideration and make an appropriate selection. Each reactor is equipped with a water vapor or inert gas bag inlet in addition to the evaporation equipment, so that the contents can be sufficiently evaporated.

In this case, as the hawking equipment, a normal hawking machine or kneader is used as appropriate depending on the nature of the contents.

In order to clarify the present invention, embodiments will be described with reference to the drawings. The raw petroleum-based virgin oil charged into the mixer 1 by x is mixed with the circulating oil from b and b' and sent to the heater 2 by the feed pump 7.

Also, water vapor is blown into this mixed oil from z. Therefore, the speed of the mixed oil in the heater tube of the heater 2 increases significantly, and the heat exchange rate improves. As a result, the temperature of the wall surface of the heater tube can be lowered, the formation of coke can be significantly reduced, and the adhesion of coke to the tube wall can be prevented.

Each reactor is equipped with a fly dressing layer and steam inert gas inlets y and y', which can sufficiently concentrate the contents, which helps prevent coke formation and prevents coke from adhering to the inner walls. It can be scraped off.

In the present invention, the petroleum heavy oil from x is mixed in the mixer 1 with circulating oil having a benzene insoluble content of 10% or more circulating from b and b' in a volume ratio of 2:1 to 1:3. Ru.

This mixed oil is passed through the heater 2 by the pump 7 and heated to 40,000 yen.
It is heated to ~46,000 ℃ and introduced into the reactor 3.

A feature of the present invention is that the flow rate in the heater and the temperature gradient in the heater can be determined by the circulation ratio of circulating oil, and by regulating this, it is possible to prevent the generation of coke. The contents of the reactor 3 are maintained at 400 to 45000, and the clear water is reinforced by introducing sufficient water vapor and, if necessary, steam or inert gas from the y, so that the benzene insoluble content of the contents is reduced to 10%. The reactions are repeated until the above is reached.

In normal cases, the average residence time in the reactor is 1 to 4 hours, and a portion is returned to the mixer 1 by the circulation pump 8 from b, and a portion is sent to the second reactor 4.

In the second reactor 4, the contents are maintained at a temperature of 400°C to 45°C, with an average residence time of 1 to 4 hours under rope reinforcement by introducing steam or inert gas from the rope layer if necessary. Time response is enhanced.

If necessary, a part of the generation part may be passed through b′ as it is or b
It is mixed with the circulating oil from and circulated to the mixer 1.

Other products are continuously removed from a as product thickeners. As described above, according to the present invention, rapid thermal decomposition and polycondensation reactions that occur during heat treatment of petroleum-based heavy oil can be properly suppressed, thereby preventing coking troubles and continuously achieving high-quality caking. It is possible to produce a drug.

In the present invention, since the petroleum heavy oil is reacted at the lowest temperature necessary for the reaction, the resulting binder contains a large amount of benzene-insoluble content, but has a small amount of quinoline-insoluble content, that is, an excellent product with a large amount of 8 resin. Has quality. Furthermore, the present invention has the feature that the quality can be adjusted by appropriately changing the reaction temperature, circulation ratio, and reaction time.

The features of the present invention are listed below.

1. Since the reaction is carried out in multiple stages, the reaction conditions are mild and control is easy.

2 A portion of the reformed car oil that has undergone a certain amount of reaction in each reactor is circulated to the mixer, which improves the thermal efficiency of the heater and reduces the temperature difference between the inside and outside of the heating tube, resulting in a rapid reaction. It is possible to prevent this and also to utilize the heat source of the circulating oil.

3. Sufficient heating is carried out by the heat sink layer attached to each reactor and steam or inert gas charging equipment, so that uniform heating is carried out and rapid reaction is prevented.

The silk agent of the present invention usually has a benzene insoluble content of 25% to 40%,
Quinoline insoluble content 12% or less, softening point (ring and ball method) 100o
It has an excellent quality of 0 or higher, and when used as a binder for molded coke or as a viscosity imparting agent, it shows excellent results and contributes as a countermeasure to the shortage of coking coal for steelmaking blast furnaces. It is possible. Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited by these examples.

Example 1 Asphalt obtained by distilling crude oil under reduced pressure using the process of the present invention with one mixer and two reactors (benzene insoluble content 0%, quinoline insoluble content 0%) 5 so/hr 1st reactor circulating oil (benzene insolubles 15.2% quinoline insolubles 5
3%) at 10%/hr using a mixer, and the reaction was carried out at a first reactor temperature of 420°C, a second reactor temperature of 410:00, and an average residence time of 2 hours.

The yield (relative to feedstock oil) and characteristic values of the obtained binder were determined as follows.
Shown in the table. Table 1 Example 2 Reactions were carried out using the same raw materials and equipment as in Example 1 and the same operations with an average residence time of 3 hours.

Table 2 shows the characteristics of the circulating oil at that time, the yield (relative to raw material oil), and characteristic values of the obtained sticky silk agent. Table 2 Example 3 Using the atmospheric residue obtained by atmospheric distillation of crude oil as a raw material, a reaction was carried out using the same equipment and operation as in Example 2. Characteristic values of the circulating oil and the obtained results Table 3 shows the yield (relative to feedstock oil) and characteristic values of the binder.

Table 3 Example 4 Asphalt obtained by distilling crude oil under reduced pressure using the process of the present invention with one mixer and two reactors (0% benzene insoluble content, 0% quinoline insoluble content) 7.5 so/ The circulating oil from the second reactor (benzene insolubles 34.5%, quinoline insolubles 10.6%) was completely mixed in a mixer for 7.5 hours/hr, and the temperature of the first reactor was 420 degrees. 2 reactor temperature 410
qo, and the reaction was carried out while keeping the average residence time at 2 hours.

The yield (relative to raw material oil) and characteristic values of the obtained binder were measured in the fourth
Shown in the table.

Table 4 Example 5 Asphalt obtained by distilling crude oil under reduced pressure using the process of the present invention with one mixer and two reactors (benzene non-falling content 0°C, quinoline insoluble content 0%) 10 pieces/ hr, the circulating oil from the second reactor (benzene insoluble content 33.4%, quinoline insoluble content 9.2%) was completely mixed in a mixer at 7 Z/hr, the first reactor temperature was 42,000, and the second reactor temperature was 410oo,
The reactions were carried out while keeping the average residence time at 4 hours in each case.

The yield (relative to raw material oil) and characteristic values of the obtained binder were measured in the fifth column.
Shown in the table. Table 5

[Brief explanation of the drawing]

The drawing is a flow sheet of an embodiment of the invention. 1... Mixer, 2... Heater, 3...
...First reactor, 4...Second reactor, 5...
・Condenser, 6... Receiver, 7... Feed pump, 8... Circulation pump, x...
Raw material blade oil inlet, y, y... Steam or inert gas inlet, z... Steam inlet, a... Product outlet, b, b'
...Modified virgin oil outlet, c, c'... Gaseous component light oil outlet, d... Light oil outlet, e.
...Gas component outlet.

Claims (1)

[Claims] 1. A method for producing a binder by heat treating petroleum-based heavy oil, in which a large number of reactors are used in series to carry out the reaction,
The method is characterized in that the reformed petroleum-based heavy oil taken out from each reactor is mixed as it is, or the reformed petroleum-based heavy oil from several reactors is mixed and mixed with the raw petroleum-based heavy oil. A method for producing a binder. 2. The benzene-insoluble content of the modified petroleum-based heavy oil mixed with the raw petroleum-based heavy oil is 10% or more, and the mixing ratio of the petroleum-based heavy oil and the modified petroleum-based heavy oil is 2: The method for producing a binder according to claim 1, wherein the ratio is 1 to 1:3. 3. The method for producing a binder according to claim 1 or 2, characterized in that the contents of each reactor are maintained at 400°C to 450°C and the reaction is carried out for 1 to 4 hours, respectively. 4. The method for producing a binder according to item 1, 2, or 3, wherein each reactor is equipped with a stirring device or a stirring device and an inert gas blowing device.