JPH0655909B2 - Soft carbon black manufacturing equipment - Google Patents

Description

The present invention relates to an apparatus for producing a soft carbon black that employs an oil furnace method. More specifically, the present invention relates to the same type of gaseous hydrocarbon and / or liquid hydrocarbon. The present invention relates to a soft carbon black manufacturing apparatus having an improved combustion chamber capable of complete combustion in a combustion chamber and controlling the aggregate size distribution of carbon black.

In the production of carbon black using the oil furnace method, generally, fuel is introduced in the axial direction or tangential direction of a cylindrical carbon black production device and burned, and this high temperature combustion gas flow is moved to the reaction zone. While
A hydrocarbon feedstock is sprayed into a hot gas stream to cause a carbon black formation reaction by incomplete combustion of the feedstock, and the carbon black hot suspension gas stream thus obtained is rapidly cooled to react. The carbon black is collected by stopping the gas and passing it through a collection device such as a cyclone or a bag filter. The powdery carbon black is shipped as a carbon black product through a granulation process and a drying process in terms of handling.

In the production of carbon black by the oil furnace method, the amount of heat required to convert the hydrocarbon feedstock sprayed in the production equipment into carbon black is supplied by partial combustion of the hydrocarbon feedstock. Inevitable,
Most of them are normally supplemented by the heat of combustion of fuel.

In known literatures such as patent publications, a gas fuel such as natural gas is generally widely used as a fuel for generating high temperature combustion gas in the oil furnace method, but liquid fuels such as crude naphtha and heavy oil are also used. It is also sometimes used.
However, different devices are usually used for the gaseous fuel combustion device and the liquid fuel combustion device, and in particular, in the liquid fuel combustion device, complete combustion is achieved by increasing the length of the combustion inlet ( There are various improvements such as, for example, Japanese Patent Publication No. 36-12766) and atomization of liquid fuel to improve the burning rate (for example, Japanese Patent Publication No. 58-27826). / Or no liquid fuel can be used in the same device.

In addition, only the superficial characteristic values such as iodine adsorption amount (evaluation of surface area) and dibutyl phthalate (DBP) absorption amount (evaluation of structure), which are the main characteristics, are included in the carbon physical properties of the rubber composition of the carbon black. It is difficult to evaluate and predict the effect, and among other characteristic values, the effect of the size distribution of aggregates (primary aggregates) on the carbon black is drawing attention.

A first object of the present invention is to use a gaseous hydrocarbon fuel and / or a liquid hydrocarbon fuel in the same combustion chamber and to completely burn them in a space outside the carbon black generation reaction system. It is an object of the present invention to provide a carbon black manufacturing apparatus in which the amount of heat contained in a flow contributes to a carbon black generation reaction. More specifically, in the first half of the combustion gas filling chamber, at least one oxygen-containing gas inlet having a central axis at a tangential position,
And at least two independent fuel fluid inlets separate from the oxygen-containing gas inlet are provided, for example, an oxygen-containing gas is introduced into the gas inlet to make the flow direction different from that of the fuel fluid. The mixing efficiency of the two fluids is remarkably improved, and in addition to that, when the hydrocarbon feedstock is sprayed by introducing the two fluids from the first half of the combustion gas filling chamber, the fuel is completely converted to fuel. It is in a soft carbon black manufacturing apparatus having a combustion gas filling chamber.

A second object of the present invention is to provide a carbon black manufacturing apparatus capable of easily controlling the aggregate size distribution of carbon black (evaluated by the frequency of Stokes equivalent diameter by centrifugal sedimentation analysis). More specifically, at least two or more oxygen-containing gas and / or fuel fluid introduction conduits are provided in the first half of the carbon black generation reaction chamber, and the carbon black is modified by changing the introduction ratio and speed of each fluid. An object is to provide a carbon black manufacturing apparatus capable of controlling the characteristics.

That is, according to the present invention, a horizontally-arranged cylindrical combustion gas filling chamber 2 and a cylindrical carbon black production reaction chamber 4 coaxially connected to the filling chamber 2 and having a larger diameter than the filling chamber 2 are provided. A raw material introduction device for introducing and spraying a hydrocarbon raw material held on the central axis of the filling chamber, a reaction continuation and rapid cooling chamber 5 coaxially connected to the end of the reaction chamber, and a rapid cooling chamber 5 after In a carbon black manufacturing apparatus 1 which is entirely lined with a refractory and is composed of a flue 6 connected to an end, (a) at least one having a central axis at a tangential position in the first half of the combustion gas filling chamber 2 Individual oxygen-containing gas inlet 9
(B) In the first half of the combustion gas filling chamber 2, at least two fuel fluid inlets 10 to 12 independent of the oxygen-containing gas inlet are installed, and (c) the combustion gas filling chamber 2 And a reaction chamber 4, a venturi portion 3 is provided, and a raw material introducing device having an outer wall provided with a heatproof cooling jacket in the central axis direction of the upstream end wall of the filling chamber 2 is attached in an insertable and withdrawable manner, The tip position of the raw material introducing device is installed on the downstream side of the oxygen-containing gas introducing port 9, and (d) in the first half of the carbon black production reaction chamber 4,
At least two or more oxygen-containing gas and / or fuel fluid inlets 13 and 14 are provided, and (e) a cooling water injection sprayer (a to g) is provided in the reaction continuation / quick cooling chamber 5 wall. It is an object of the present invention to provide a soft carbon black manufacturing apparatus characterized in that a plurality of water spraying parts of g) are installed in the chamber 5 so that they can be inserted and pulled out freely.

Next, the present invention will be described in more detail with reference to the accompanying drawings.

FIG. 1 is a vertical sectional front view of an example of the present invention.
The drawing is a sectional view taken along the line AA of FIG.

FIG. 3 is a cross-sectional view of another aspect taken along the line AA of FIG. 1, and FIG. 4 is a cross-sectional view taken along the line BB of FIG.

In the carbon black manufacturing apparatus shown in FIGS. 1 and 2, a bench lily 3 is coaxially connected to a horizontally-arranged cylindrical combustion gas charging chamber 2, then a reaction chamber 4, and a reaction continuation rapid cooling chamber 5, The flue 6 is sequentially connected to the end.

A guide 7 with a water-cooled jacket for a hydrocarbon raw material introducing device (not shown) is inserted and fixed in an insertion opening provided in the combustion gas filling chamber 2 through a front end wall of the central axis of the combustion gas filling chamber 2. Fittings for fixing the raw material introducing device, for example, set screws 8 and 8 ', are attached. Since the feed oil introduction position has a great influence on the size distribution of the carbon black aggregates and the carbon black conversion rate as described above, it is desirable that the position can be freely moved. For this purpose, the introduction device is provided with a heat insulating cooling jacket on the outer wall so that it can be inserted and withdrawn even in the combustion gas. Further, in the first half portion of the combustion gas filling chamber 2, two oxygen-containing gas introduction ports 9 and 9'having a central axis at a tangential position thereof are arranged so as to face each other. From the outer periphery of the side wall, the oxygen-containing gas introduction port 9,
As shown in FIG. 2, six fuel fluid inlets (10, 10 ′, 11, 11 ′, 12) which flow into the filling chamber 2 are formed in the space formed by the vertical cross-sections at the diameter ends of 9 ′. , 12 ') are symmetrical on the circumference and the oxygen inlets 9, 9'
It is installed separately from and independently. At least two fuel fluid inlets may be installed from the outer peripheral portion of the filling chamber 2 such as 10, 10 ', but as shown in the figure, six (10-
12 ') is desirable, and at most 8 can sufficiently achieve the purpose.

As described above, the combustion gas filling chamber 2 is provided with the oxygen-containing gas inlets 9 and 9'in the tangential direction and the separate fuel fluid inlets (10 to 12 ') independent of the inlets. The fuel fluid inlets (10 to 12 ') circulate in the radial direction of the circumference toward the central axis of the filling chamber 2. The oxygen-containing gas and the fuel fluid are introduced into the filling chamber 2 in different introduction directions and as independent flows, and the difference and independence of the flow directions significantly increase the mixing efficiency of the oxygen-containing gas and the fuel fluid. It leads to an increase in burning rate. Further, the fuel fluid introduced from the fuel fluid inlets 10 and 10 'adjacent to the oxygen-containing gas inlets 9 and 9'is effectively mixed with the oxygen-containing gas and burns while the fuel is present on the downstream side in the swirling direction. Fluid introduction pipe 11,
The mixing of the fuel fluids introduced from 11 'and 12, 12' is promoted, and the flame propagation effect of the fuel fluids makes it possible to achieve complete conversion of the fuel fluids in a short time.

By locating the oxygen-containing gas introduction ports 9 and 9'and the fuel fluid introduction ports 10 to 12 'in the forehead rather than the longitudinal center of the filling chamber 2 and the synergistic action of the above effects, the filling chamber 2 The fuel combustion is completed in the forehead without making the size too large. Further, the number and the amount of the fuel fluid inlets can be easily changed, and the fuel load factor (heat generation amount per unit volume) in the combustion gas filling chamber 2 can be easily controlled. It has the advantage of being applicable to manufacturing.

The bench lily 3 in the present invention can be a throat portion having a diameter considerably larger than the throat portion in comparison with the diameter of the combustion chamber (combustion gas filling chamber in the present invention) in the conventional hardware-based manufacturing apparatus. The ratio D / C of the diameter (D) of the throat portion to the diameter (C) of the filling chamber 2 is preferably 0.4 or more and 0.75 or less. In relation to the D / C ratio, the cone angle of the frustoconical inlet of the bench lily 3 is 100
~ 160 degrees, preferably 110-140 degrees. That is, in the present invention, the conical surface of the bench lily inlet portion, which has a large D / C ratio as described above but should also be called the outlet of the combustion gas filling chamber 2, has a steep slope with respect to the central axis, and the flow of the combustion gas is throat portion. As it is rapidly concentrated and made to flow, the feedstock hydrocarbons introduced and sprayed upstream of the bench lily inlet carry out a more uniform blackening reaction in comparison with conventional equipment in the disturbance and contact with the combustion gas. You can do it. Therefore,
If the cone angle at the entrance of the bench lily exceeds 160 degrees, the concentrated flow of combustion gas to the throat will not be performed smoothly, which is unsatisfactory. If it falls below 100 degrees, the initiation or promotion region of the carbon blackening reaction will be slowed down. It becomes difficult to control only a part. Whether it can be controlled to position the reaction start point in such a throat,
It can be easily grasped by measuring the degree of temperature drop in this portion. The frusto-conical shape at the outlet of the bench lily does not have to be angularly limited, but it is preferable to connect it to the inlet of the reaction chamber 4 with a smooth low angle of 30 to 60 degrees. In short, the bench lily 3 according to the present invention is connected to the throat portion at a steep angle at its inlet, so if the length is adjusted, L / 5 to L / 3 with respect to the length (L) of the combustion gas charging chamber 2. It is desirable to set the length of the throat portion, and it is not necessary to increase the length of the throat portion, and D / 5 to D / 2 is satisfied. The length of the bench lily outlet is preferably about L / 3 to 2L / 3.

The diameter of the reaction chamber 4 in the present invention can be changed within a range larger than the diameter of the combustion gas filling chamber 2 depending on the grade to be manufactured, but it is preferably 1.5 to 4 times the throat diameter (D). is there. Then, a reaction chamber 4 and a reaction continuation / quick cooling chamber 5 are connected to the rear part thereof. The diameter of the chamber 5 can be the same until the flue 6 is reached.

FIG. 3 shows another mode as seen from the arrow AA of FIG. 1, and shows the gas inlets 9 and 9 ′ of the combustion gas filling chamber 2.
The fuel combustion devices 21 and 21 'are installed at the central axis positions of the fuel cells. Further, the oxygen-containing gas for fuel combustion is introduced coaxially as a flow surrounding the fuel combustion device 21, 21 ', but the oxygen-containing gas is introduced tangentially to the gas introduction port 9, 9'. You can also The fuel combustion device 21, 21 'used here is preferably equipped with a water-cooling or air-cooling type heat-insulating cooling jacket as previously proposed (Japanese Patent Publication No. 58-27826 and attached FIG. 2). The fuel fluid is radially introduced into the filling chamber 2 through the penetration inlets 11 and 1 '.

It is also one of the features of the present invention that at least two or more introducing pipes for introducing the oxygen-containing gas and / or the fuel fluid are provided in the first half portion of the carbon black generation reaction chamber 4.

As shown in FIG. 1 and FIG. 4, this inlet pipe is located in the first half of the reaction chamber 4, preferably, the center position of the inlet is within 1.5 times the diameter of the reaction chamber 4 from the outlet end of the bench lily,
13 ', 13 "and 13 are installed in parallel and tangentially through the upper and lower ends of the reaction chamber 4. Control of the introduction amount of the oxygen-containing gas and / or fuel fluid into these introduction pipes and swirling direction Changed (13-13 ″ use inlet and 13′-13
The use of the inlet), and further the use of the 14-14 inlet of the similar structure provided on the downstream side of the 13-13 inlet,
It can be used as one of the means for controlling the carbon black aggregate size distribution while maintaining the quality characteristics such as iodine adsorption amount and dibutyl phthalate absorption amount at substantially the same level.

In addition to this, the installation of the cooling water injection sprayers a to g in the rapid cooling chamber 5 for continuing the reaction as shown in FIG. 1 allows the expansion and contraction of the reaction chamber region to be freely performed, and the reaction chamber for each product type can be freely set. Since the region can be set freely, the flow of the hot suspension gas flow in the reaction zone and the cooling zone of the production equipment reaction zone and cooling zone can be adjusted by adjusting the cooling operation conditions to the introduction position together with the adjustment of the cooling water injection amount per unit time. Since the (velocity) state and the pressure state can be changed together with the cooling rate, it can be used as another control means for changing the carbon black aggregate size distribution.

Operating conditions 13 to 13 and 14 to 14 in the reaction chamber 4,
By appropriately selecting the operating position of the cooling water injection sprayer in the reaction continuation / quick cooling chamber 5, a wide range of soft carbon black can be manufactured, and the aggregate size distribution can be easily controlled.

Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 A GPF grade carbon black was manufactured using a manufacturing apparatus having the same structure as shown in FIG. 1 and FIG. The dimensions of each component of this manufacturing apparatus are as follows.

Combustion gas filling chamber (2) Inner diameter …… 400mmφ Length …… 200mm Oxygen-containing gas inlet (9,9 ′) Inner diameter …… 80mmφ Center position …… 100mm from front end of combustion gas filling chamber (2) Fuel fluid introduction Mouth inner diameter …… 20mmφ 6 pieces Installation position …… Symmetrically installed radially on the circumference of the combustion gas filling chamber (2) Bench lily inlet length …… 50mm (cone angle: 127 degrees) Throat diameter …… 200mmφ throat Length …… 80mm Outlet length …… 100mm (Cone angle: 45 degrees) Reaction chamber (4) Diameter …… 500mmφ Gas inlet (13-13,14〜14) Diameter …… 40mmφ Center position …… Bench lily outlet end The 100 mm and 300 mm combustion gas filling chambers (2) are equipped with a water-cooled guide on the central axis, followed by a water-cooled jacket guide for heat insulation cooling, and a raw material introduction device equipped with a water cooling jacket for heat insulation cooling. Inserted in the guide. In addition, a cooling water injection sprayer is provided at the insertion port marked with symbols a to g in the rapid cooling chamber 5 for continuing the reaction.
No. 47 (Applicant: Asahi Carbon Co., Ltd.)].

As the raw material hydrocarbon, one having the properties and composition as shown in Table 1 was used.

Natural gas was used as the fuel fluid. The carbon black manufacturing device was operated as shown in Table 2.

Example 2 A GPF class carbon black with controlled aggregate size characteristics was manufactured using a manufacturing apparatus having the same structure and dimensions as those shown in Example 1. The manufacturing conditions are as shown in Table 5, and the conditions not mentioned were the same as those in Table 2.

The characteristics of the carbon blacks obtained in Examples 1 and 2 and Comparative Example 1 are summarized in Table 4.

As is clear from the results of Table 4, in Comparative Example 1, the feedstock hydrocarbon oil introduction position is the oxygen-containing gas introduction port 9
The aggregate size distribution index s was large because it was on the upstream side of the diameter of, and a decrease in the yield per feed oil was observed as compared with Examples 1 and 2.

The carbon black aggregate size of Dst and s by sedimentation analysis shown in Table 4 (CB aggregate size)
Was measured as follows.

Equipment used Disk Centrifuge (Photo sedimentometer) (DCF) (UK) Joyce Loebl measurement method 0.05 ~ 0.1% carbon black was added to a 30% methanol aqueous solution with some surfactants, and sonicated. To completely disperse.

15 v / v% glycerin aqueous solution sedimentation solution (spin solution) 20
Rotation speed of the rotating disk with ~ 30ml added is 8000
Adjust to rpm and add 0.02-0.03 ml of the above dispersion.

At the same time as adding the dispersion liquid, the recorder is operated to pass a fixed point near the outer circumference of the rotating disk by sedimentation CB agg
Optically measure the amount of regate and record it as a histogram over time.

Settling time can be calculated by the following formula (General type of Stokes formula)
Convert to okes equivalent diameter and obtain a histogram of CBaggregate's Stokes equivalent diameter and its frequency.

In the equation (1), d is the Stokes equivalent diameter of CBaggregate that passes through the optical measurement point of the rotating disk at time t after the start of sedimentation.

The constant K is the amount of the spin liquid at the time of measurement, the viscosity, and the density difference with the carbon black (the true density of the carbon black is 1.86).
g / ml), and is a constant determined by the rotation speed of the rotating disk. For example, 15v / v as spin liquid
% Value of glycerin aqueous solution 17.5ml, K value is 368.9 when measuring temperature 20 ℃ and disk rotation speed 8000rpm.
d is displayed in nm and t is displayed in minutes. Definition of Dst and s In the Stokes equivalent diameter histogram of the aggregate obtained by the above measurement operation, St giving the highest frequency (actually, the maximum absorbance because optical measurement is performed)
The diameter equivalent to okes is called Dst (Mode), and is used as a measure of the average size of CBaggregate.

Further, in the histogram, when the frequency (absorbance) that is half the frequency (absorbance) indicated by Dst is shown and the Stokes equivalent diameter larger than Dst is ▲ ^DL ₅₀ ▼,
The aggregate size distribution index s is defined by s = 0.84932 × Log (▲ D ^L ₅₀ ▼ / Dst). This is a measure of the distribution width of a relatively large aggregate size.

Example 3 An SRF grade carbon black was manufactured using a manufacturing apparatus having the same structure as shown in FIGS. 1 and 3. The dimensions of each component of this manufacturing apparatus were as follows.

Combustion gas inlet (9, 9 ') Inner diameter ...... 100mmφ Center position ...... 50mm from the front end of combustion gas filling chamber (2) Fuel fluid inlet Inner diameter ...... 20mmφ 2 pieces Installation position ...... Combustion gas filling chamber (2 The components having the same dimensions as those shown in Example 1 were used for the other components, and the composition of the feedstock hydrocarbon oil was also the same as that of Example 1. The manufacturing conditions at this time were as shown in Table 7.

The physicochemical properties of SRF grade carbon black produced under these conditions are IA 22.3mg / g, DBPA 62.4ml / 100g, Dst 290nm, s
It was 0.184.

The feed position for the raw hydrocarbon oil is 11
The physicochemical properties of the SRF grade carbon black of Comparative Example 2 provided at a position of 0 mm and manufactured as in Example 3 are
2.7mg / g, DBP64.1ml / 100g, Dst 283, s0.203. Since the feedstock hydrocarbon oil introduction position is upstream of the diameter of the oxygen-containing gas introduction port 9, the aggregate size distribution index s is calculated. It became larger than Example 3.

[Brief description of drawings]

FIG. 1 is a vertical sectional front view of an example of an apparatus adopted in the present invention, and FIG. 2 is a sectional view taken along the line AA of FIG. 3 is a sectional view of another embodiment taken along the line AA of FIG. 1, and FIG. 4 is a sectional view taken along the line BB of FIG. 1 ... Carbon black manufacturing equipment 2 ... Combustion gas filling chamber, 3 ... Bench lily unit 4 ... Reaction chamber, 5 ... Reaction continuation and rapid cooling chamber 6 ... Flue, 7 ... Guide with water cooling jacket 8 ... … Set bis, 9,9 ′ …… Oxygen-containing gas inlet 10,10 ′, 11,11 ′, 12,12 ′ …… Fuel fluid inlet 13-13,14〜14 …… Inlet 21,21 ′… … Fuel combustion device a ～ g …… Cooling water injection sprayer insertion port

Claims (5)

[Claims] 1. A horizontally-arranged cylindrical combustion gas charging chamber 2
And coaxially connected to the filling chamber 2 and the filling chamber 2
A cylindrical carbon black producing reaction chamber 4 having a larger diameter than the above, a raw material introducing device for introducing and spraying a hydrocarbon raw material held on the central axis of the filling chamber, and coaxially connected to the end of the reaction chamber. In the carbon black manufacturing apparatus 1 which is entirely lined with a refractory and comprises a reaction continuation / quick cooling chamber 5 and a flue 6 connected to the rear end of the rapid cooling chamber 5, (a) charging with the combustion gas At least one oxygen-containing gas inlet 9 having a central axis is provided at a tangential position in the first half of the chamber 2, and (b) in the first half of the combustion gas filling chamber 2, at least independent of the oxygen-containing gas inlet. Two fuel fluid inlets 10 to 12 are installed, (c) a venturi portion 3 is provided between the combustion gas filling chamber 2 and the reaction chamber 4, and the central axis direction of the upstream end wall of the filling chamber 2 Install a heat insulation cooling jacket on the outer wall The raw material introducing device is attached so as to be insertable and withdrawable, and the tip position of the raw material introducing device is installed on the downstream side of the oxygen-containing gas introducing port 9, and (d) at least in the first half of the carbon black production reaction chamber 4. Two or more oxygen-containing gas and / or fuel fluid introduction ports 13 and 14 are provided, and (e) the cooling water injection sprayer (a to g) is provided in the wall of the rapid cooling chamber 5 for continuing the reaction and the sprayer (a to g). 2. A soft carbon black manufacturing apparatus, characterized in that a plurality of water spraying parts of (1) are installed in the chamber 5 so that they can be inserted and pulled out freely. 2. The soft carbon black production apparatus according to claim 1, wherein an oxygen-containing gas introduction pipe is connected to the oxygen-containing gas introduction port 9 in the first half of the combustion gas filling chamber 2. 3. A substantially cylindrical combustion gas generation chamber is installed at an oxygen-containing gas introduction port 9 in the first half of the combustion gas filling chamber 2, and a fuel combustion device is provided at a central axis position of the combustion gas generation chamber.
The soft carbon black production apparatus according to claim 1, wherein 21 is inserted and held. 4. The fuel fluid inlets 10 to 12 in the first half of the combustion gas filling chamber 2 are radially arranged on the circumference of the filling chamber 2 according to any one of claims 1 to 3. The soft carbon black production apparatus described. 5. The center position of the inlets 13 and 14 of the first half of the carbon black production reaction chamber 4 is located within 1.5 times the diameter of the reaction chamber 4 from the venturi 3 outlet.
Item 5. The soft carbon black production apparatus according to any one of items 4 to 4.