CN103289719B

CN103289719B - Process for preparing asphalt sphere

Info

Publication number: CN103289719B
Application number: CN201310227822.9A
Authority: CN
Inventors: 李开喜
Original assignee: Shanxi Institute of Coal Chemistry of CAS
Current assignee: Shanxi Institute of Coal Chemistry of CAS
Priority date: 2013-06-08
Filing date: 2013-06-08
Publication date: 2014-11-26
Anticipated expiration: 2033-06-08
Also published as: CN103289719A

Abstract

The invention relates to a process for preparing an asphalt sphere, and the process comprises the following steps of: placing asphalt into a high-pressure kettle by placing 0.2-0.4 kilograms of the asphalt into each 1 liter of volume of the high-pressure kettle; then introducing air by introducing 10-20 liters of the air to each kilogram of the asphalt per hour; then increasing temperature; starting to stir at the stirring speed of 200-400 rpm (revolutions per minute) when the temperature is increased to 150-200 DEG C; continuously increasing the temperature to 300-380 DEG C, and oxidizing for 1-5 hours; then reducing the temperature of the high-pressure kettle to 180-250 DEG C while stirring, adding naphthalene which accounts for 20wt%-35wt% of the asphalt, stirring at the temperature for 1-3 hours, and then reducing the temperature to 80-95 DEG C; then adding a dispersing agent which accounts for 0.1%-1% of the weight of the asphalt to the high-pressure kettle, adding water to 60%-80% of the volume of the high-pressure kettle at the same time, stirring at 100-150 DEG C at the rotation speed of 300-500 turns/minute for 1-5 hours, then reducing the temperature to room temperature, and carrying out solid-liquid separation to obtain the asphalt sphere of 0.5-1.5 mm. The process disclosed by the invention is pollution-free and can directly complete the process for preparing the asphalt sphere in a same reaction kettle without crushing or extruding strips.

Description

Bitumen ball preparation technology

Technical field

The invention belongs to a kind of preparation technology of bitumen ball.

Background technology

Spheric active carbon is a kind of important absorbent charcoal material, and compared with the gac of other types, the research report of ball-type gac is less, especially sphere diameter be the millimetre-sized spheric active carbon taking pitch as raw material still less.What prepare this spheric active carbon is pitch containing carbon matrix precursor, needs first pitch to be carried out being prepared as bead by emulsification method again after modification, and the modification of pitch and balling-up become indispensable step for this reason.

The patent of preparing grade spheric active carbon taking pitch as presoma is more, Chinese invention patent 03178572 " is rich in the preparation method of the asphalt-base globular active carbon of mesopore " and is pitch, the atmospheric oxidation of coal tar wet goods are obtained adding aromatic hydrocarbon small molecules to carry out modification to it after the pitch of softening temperature 200-300 DEG C again, afterwards by adding dispersion agent to make balling-up pitch, final emulsion balling-up, makes bitumen ball thereby also need to obtain the emulsification balling-up that balling-up pitch just can carry out next step; It is by heavy hydrocarbon oil level raw materials such as the residues of petroleum tar, coal tar, low softening point asphalt or petroleum naphtha ethene processed that Chinese invention patent 200410100531 " is prepared the method for spherical activated carbon ", by using oxygenant as HNO ₃, air etc. is oxidized and makes oxidized bitumen, carries out modification afterwards with the aromatic hydrocarbons of naphthalene one class, and at a certain temperature extrusion, be broken into clavate fragment, then emulsification balling-up.Visible, its pitch for balling-up is the fragment after fragmentation; Chinese invention patent 200610127621 " a kind of method of preparing the ball shape active carbon that heavy metal content is low ", Chinese invention patent 200810035853 " a kind of preparation method of nitrogen-containing asphalt-base spherical activated " and Chinese invention patent 201210317727 " the low power consuming preparation method of asphalt-base spherical activated carbon " etc. all need the pitch that makes in advance balling-up could finally obtain corresponding bitumen ball, so virtually not only need many complete equipments but also technological process is lengthened, simultaneously inevitable generation environmental pollution in acquisition balling-up pitch process.

Summary of the invention

The object of this invention is to provide one pollution-free, directly in same set of reactor, complete without fragmentation or extrusion the technique of preparing bitumen ball.

Preparation technology of the present invention realizes as follows:

In long-pending by every 1 liter of autoclave body, put into the pitch of 0.2-0.4 kilogram weight, pitch is put into autoclave, the air capacity rising by the per kilogram pitch 10-20 of needs per hour afterwards passes into air, then heat up, in the time that temperature is raised to 150-200 DEG C, opens and stir, stir speed (S.S.) is 200-400 rev/min, continues to be warmed up to 300-380 DEG C and is oxidized 1-5h; Autoclave under agitation cools to 180-250 DEG C afterwards, adds the naphthalene of pitch weight 20-35%, at this temperature, stirs 1-3h, then cools to 80-95 DEG C; Again the dispersion agent of pitch weight 0.1-1wt% is added to autoclave, water is joined to the 60-80% of autoclave volume simultaneously, at 100-150 DEG C, to cool to room temperature after the rotating speed stirring 1-5h of 300-500 rev/min, solid-liquid separation obtains the bitumen ball of 0.5-1.5mm.

The present invention's pitch used is that softening temperature is 35～75 DEG C of soft pitches, 75～95 DEG C of mid-temperature pitches or 95～120 DEG C of hard pitches.

Dispersion agent as above is polyvinyl alcohol, polyoxyethylene glycol or octadecyl sodium sulfonate.

Advantage of the present invention:

(1) all reaction masses all react in same set of equipment, and its utilization ratio is greatly improved, very favourable to reducing production costs;

(2) owing to operating in same set of reactor, can not produce a large amount of waste gas and waste residue, alleviate environmental stress;

(3) the present invention all operates in a set of reactor, and floor space reduces greatly, and equipment cost significantly reduces.

Embodiment

Embodiment 1

The soft pitch of putting into 35～75 DEG C of softening temperatures of 4 kilograms in 10 liters of autoclaves, blasts 40 liters/h air, then heats up, and in the time that temperature is raised to 150 DEG C, opens and stirs, and stir speed (S.S.) is 200 revs/min, continues to be warmed up to 300 DEG C and is oxidized 5h; Reactor under agitation cools to 180 DEG C afterwards, add 0.8 kilogram of naphthalene, at this temperature, stir 3h, then cool to 80 DEG C, now add the polyvinyl alcohol of asphalt quality 1wt%, water is joined simultaneously kettle long-pending 60%, cool to room temperature stir 1h with the rotating speed of 300 revs/min at 150 DEG C after, solid-liquid separation obtains bitumen ball.The sphere diameter of gained bitumen ball more than 90% is 1.5mm, and sphericity reaches 95%.

Embodiment 2

The hard pitch of putting into 95～120 DEG C of softening temperatures of 20 kilograms in 100 liters of autoclaves, blasts 400 liters/h air, then heats up, and in the time that temperature is raised to 200 DEG C, opens and stirs, and stir speed (S.S.) is 300 revs/min, continues to be warmed up to 350 DEG C and is oxidized 3h; Reactor under agitation cools to 230 DEG C afterwards, add 7 kilograms of naphthalenes, at this temperature, stir 3h, then cool to 90 DEG C, now add the octadecyl sodium sulfonate of asphalt quality 5wt%, water is joined simultaneously kettle long-pending 70%, cool to room temperature stir 3h with the rotating speed of 400 revs/min at 120 DEG C after, solid-liquid separation obtains bitumen ball.The sphere diameter of gained bitumen ball more than 92% is 1.1mm, and sphericity reaches 93%.

Embodiment 3

The mid-temperature pitch of putting into 75～95 DEG C of softening temperatures of 400 kilograms in 1000 liters of autoclaves, blasts 6000 liters/h air, then heats up, and in the time that temperature is raised to 180 DEG C, opens and stirs, and stir speed (S.S.) is 400 revs/min, continues to be warmed up to 380 DEG C and is oxidized 1h; Reactor under agitation cools to 250 DEG C afterwards, add 120 kg naphthalene, at this temperature, stir 2h, then cool to 95 DEG C, now add the polyoxyethylene glycol of asphalt quality 10wt%, add simultaneously water to kettle long-pending 80%, cool to room temperature stir 5h with the rotating speed of 500 revs/min at 100 DEG C after, solid-liquid separation obtains bitumen ball.The sphere diameter of gained bitumen ball more than 92% is 0.5mm, and sphericity reaches 97%.

Embodiment 4

The soft pitch of putting into 35～75 DEG C of softening temperatures of 20 kilograms in 50 liters of autoclaves, blasts 300 liters/h air, then heats up, and in the time that temperature is raised to 160 DEG C, opens and stirs, and stir speed (S.S.) is 250 revs/min, continues to be warmed up to 320 DEG C and is oxidized 2h; Reactor under agitation cools to 220 DEG C afterwards, add 5 kilograms of naphthalenes, at this temperature, stir 2h, then cool to 90 DEG C, now add the polyoxyethylene glycol of asphalt quality 3wt%, add simultaneously water to kettle long-pending 75%, cool to room temperature stir 3h with the rotating speed of 400 revs/min at 120 DEG C after, solid-liquid separation obtains bitumen ball.The sphere diameter of gained bitumen ball more than 92% is 1.1mm, and sphericity reaches 92%.

Embodiment 5

The hard pitch of putting into 95～120 DEG C of softening temperatures of 180 kilograms in 500 liters of autoclaves, blasts 3000 liters/h air, then heats up, and in the time that temperature is raised to 190 DEG C, opens and stirs, and stir speed (S.S.) is 400 revs/min, continues to be warmed up to 340 DEG C and is oxidized 2h; Reactor under agitation cools to 250 DEG C afterwards, add 50 kilograms of naphthalenes, at this temperature, stir 2h, then cool to 85 DEG C, now add the octadecyl sodium sulfonate of asphalt quality 8wt%, add simultaneously water to kettle long-pending 65%, cool to room temperature stir 2h with the rotating speed of 450 revs/min at 130 DEG C after, solid-liquid separation obtains bitumen ball.The sphere diameter of gained bitumen ball more than 94% is 0.8mm, and sphericity reaches 94%.

Embodiment 6

The mid-temperature pitch of putting into 75～95 DEG C of softening temperatures of 4 kilograms in 10 liters of autoclaves, blasts 72 liters/h air, then heats up, and in the time that temperature is raised to 170 DEG C, opens and stirs, and stir speed (S.S.) is 350 revs/min, continues to be warmed up to 350 DEG C and is oxidized 2h; Reactor under agitation cools to 200 DEG C afterwards, add 1.4 kilograms of naphthalenes, at this temperature, stir 3h, then cool to 90 DEG C, now add the polyvinyl alcohol of asphalt quality 6wt%, add simultaneously water to kettle long-pending 60%, cool to room temperature stir 2h with the rotating speed of 400 revs/min at 120 DEG C after, solid-liquid separation obtains bitumen ball.The sphere diameter of gained bitumen ball more than 90% is 1.2mm, and sphericity reaches 95%.

Claims

1. a bitumen ball preparation technology, is characterized in that comprising the steps:

In long-pending by every 1 liter of autoclave body, put into the pitch of 0.2-0.4 kilogram weight, pitch is put into autoclave, the air capacity rising by the per kilogram pitch 10-20 of needs per hour afterwards passes into air, then heat up, in the time that temperature is raised to 150-200 DEG C, opens and stir, stir speed (S.S.) is 200-400 rev/min, continues to be warmed up to 300-380 DEG C and is oxidized 1-5h; Autoclave under agitation cools to 180-250 DEG C afterwards, adds the naphthalene of pitch weight 20-35%, at this temperature, stirs 1-3h, then cools to 80-95 DEG C; Again the dispersion agent of pitch weight 0.1-1wt% is added to autoclave, water is joined to the 60-80% of autoclave volume simultaneously, at 100-150 DEG C, to cool to room temperature after the rotating speed stirring 1-5h of 300-500 rev/min, solid-liquid separation obtains the bitumen ball of 0.5-1.5mm;

Described pitch is that softening temperature is 35～75 DEG C of soft pitches, 75～95 DEG C of mid-temperature pitches or 95～120 DEG C of hard pitches;

Described dispersion agent is polyvinyl alcohol, polyoxyethylene glycol or octadecyl sodium sulfonate.