CN1086518A - Organosilicon cyclic body prepared by silastic atmospheric cracking - Google Patents
Organosilicon cyclic body prepared by silastic atmospheric cracking Download PDFInfo
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- CN1086518A CN1086518A CN 92112510 CN92112510A CN1086518A CN 1086518 A CN1086518 A CN 1086518A CN 92112510 CN92112510 CN 92112510 CN 92112510 A CN92112510 A CN 92112510A CN 1086518 A CN1086518 A CN 1086518A
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- ring body
- organosilicon
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- silicone rubber
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Abstract
The present invention is the manufacture method that the silicon rubber atmospheric cracking is produced the organosilicon ring body, belongs to the chemical industry comprehensive utilization of waste silicone rubber.The present invention is to be raw material with silastic product leftover bits, waste silicone rubber, through washing, pulverize, and under 200 ℃～500 ℃ the temperature and the condition of catalyst, atmospheric cracking safety in production organosilicon ring body.Outstanding advantage of the present invention is that processing unit is simple, low, the average once through yield height of electric heating unit consumption, operational safety, can make things convenient for, and produces continuously or discontinuously economically.
Description
The present invention relates to the chemical industry comprehensive utilization of waste silicone rubber, is the manufacture method that a kind of atmospheric cracking silicon rubber prepares the organosilicon ring body.
Current, silicon rubber shared proportion in whole world organosilicon product surpasses 50%, the leftover bits of silastic product, the accumulating amount of waste silicone rubber are also more and more, and these waste silicone rubber major parts are dropped or are only pulverized and do filler, are used for laying road or are used for building waterproof layer.Produce hexamethyl cyclotrisiloxane (D as for directly adopting waste silicone rubber industrialization ground cracking to fall consor
3), the organosilicon ring bodies such as siloxanes of octamethylcyclotetrasiloxane and other big ring, do not meet reported in literature so far as yet.
The objective of the invention is directly to adopt waste silicone rubber is raw material, comprises sulfuration or not sulfuration, contains filler or does not contain the various waste silicone rubbers of filler, and atmospheric cracking is produced the organosilicon ring body.
To achieve these goals, it is poly-that the present invention adopts catalysis to fall, and normal pressure splits Jie's technology.Select for use sulfuration or the sulfuration various waste silicone rubbers that contain filler or do not contain filler be raw material, under the temperature condition of catalyst and 150 ℃～500 ℃, atmospheric cracking methylsiloxane circlewise prepares the organosilicon ring body.At first waste silicone rubber is cleaned up and drain, be ground into fritter or sheet (being used) if silicon rubber viscous fluid or gel also can directly be sneaked into pulverizer; To be cut into small pieces again or flaky silicon rubber and the abundant mix of catalyst, and make the surface of silicon rubber be stained with catalyst equably.Catalyst adopts normally used alkali metal hydroxide or its aqueous solution (concentration is 28～35%).The consumption of catalyst is generally 3～8% of silicon rubber weight of material, 0.2～1.2% of its consumption of adding surperficial dirt agent in the catalyst.Behind silicon rubber and the even mix of catalyst,, under normal pressure, split Jie's methylsiloxane circlewise from the top mouth charging of scission reaction stove.
The scission reaction stove adopts the vertical structure of blank pipe, can be that single tube also can be a multitube, and how much this can deciding according to reaction mass.
Guan Gaowei 1～the 2m of scission reaction stove, the useful volume of blank pipe is at 0.8m
3More than, around the resistance wire heating, whole scission reaction stove is divided into 2～3 heating zones outward, and the temperature of each heating zone is controlled between 150 ℃～500 ℃, and guarantees to increase piecemeal from epimere to hypomere temperature.Industrially, pyrolysis can be divided into 3 heating zones for being made full use of.Epimere is a preheating section, and temperature is controlled at about 150 ℃～200 ℃; The stage casing is preceding conversion zone, and temperature is controlled at about 200～400 ℃; Hypomere is the afterreaction section, and temperature is controlled at about 300～500 ℃.In the middle of the pipe material stirring rod is housed, is used for ash discharge and loosening gas circuit.Be mixed with the material of catalyst equably, from the charging opening of Reaktionsofen, add, the material steam that reaction generates is discharged from the material steam exit of Reaktionsofen downside, the pressure that reacted residual ash leans on gravity to reach when feeding in raw material moves down automatically, discharge from the ash output hole of Reaktionsofen bottom, ash output hole immerses in the water, and ashes directly enters in the water.
From scission reaction furnace bottom side, the reactant that material vapor outlet port place discharges after the condensation, can obtain organosilicon hybrid ring body through dust discharge.
This mixed methylcyclosiloxane contains moisture, uses water-and-oil separator, and water layer is discharged from the bottom, and oil reservoir is discharged by the top, and this oil reservoir is the organosilicon ring body.After measured, it includes the hexamethyl cyclotrisiloxane (D more than 30%
3), the octamethylcyclotetrasiloxane more than 40%, D
3～D
7The total content that is hexamethyl cyclotrisiloxane-tetradecamethylcycloheptasiloxane reaches 90%.This organosilicon hybrid ring body is produced various high-quality organosilicon products through being directly used in from powder system only.Residual ash after the scission reaction and fail the material piece of complete reaction because of its surface is mixed with the organosilicon thing equably, can directly be recycled.
Adopt the method for atmospheric cracking to produce organosilicon hybrid ring body, operational safety, efficient height, the electric heating unit consumption is low, processing unit simple, can make things convenient for, economically suitability for industrialized production.
Fig. 1 makes the schema of organosilicon hybrid ring body for silicon rubber cracking.
Fig. 2 is a scission reaction stove sectional view.
The reaction process flow process is schematically as follows:
The raw material catalyst
↓ ↓
Washing → pulverizing → batching → reaction → dedusting → condensation → separation → organosilicon hybrid ring body
As shown in Figure 1, material (1) is put into rinsing bowl (2) washing, through pulverizer (3) fragmentation, sneaks into alkali metal hydroxide or its aqueous solution in material, and surfactant. Evenly mix and stir in agitator (4), put into cracking reaction stove (5) by the material mouth then, the material steam that reaction generates is discharged from the material steam exit of reacting furnace. Through deduster (6) and condenser (7), discharge and obtain organosilicon hybrid ring body.
The present invention is illustrated with embodiment below in conjunction with accompanying drawing.
Example one: the example of single tube reactor.
As accompanying drawing 2, the scission reaction stove is a single tube reactor.Adopt directly through Φ 4 ", the steel pipe of long 1000mm.Useful volume 8 liters of blank pipe (9).The outside nichrome wire that twines divides three sections (10), (11), (12) to control three sections Heating temperatures respectively by voltate regulator.Epimere (10) is controlled at about 150 ℃, and stage casing (11) are controlled at 200～400 ℃, hypomere (12) and are controlled at 300～500 ℃; Reactor downside material steam exit (13) is connected to fly-ash separator and prolong.Ash output hole (14) immerses in the water.5kg thickness be the sheet waste silicone rubber of 5mm after washing drains, be cut into the random small pieces of 2～3mm.Sneak into the tensio-active agent that weight is about 6% potassium hydroxide aqueous solution (concentration is 30%) of silicon rubber weight and is about 3g in material, the three evenly mixes and stirs in agitator.Then adopt interruption method or uninterrupted not reinforced method from charging opening (7) charging of scission reaction stove, heat gradually and react.With loosening material gas circuit of material stirring rod (8) and ash discharge.Initial reaction is more violent, then tends to be steady.Have white cigarette discharge at material vapor outlet port place (13), through dedusting, condensation, separate with oil-water separator, the upper strata is an organosilicon hybrid ring body, and lower floor is a water.Obtain the thick oily 2.4kg of organosilicon hybrid ring body, recovery per pass reaches 48%.
Example two: the example of two-tube reactor
Prepare a two-tube reactor, its useful volume 200 liters.Reactor head is provided with charging opening, and with the material stirring rod.The reactor bottom reducing is immersed in the water, and ash confusingly directly enters in the water.Raw material select for use mix liquid state is arranged, the organosilicon superpolymer of gel state, adhesion attitude, and the waste silicone rubber that is mingled with the residual ash of part scission reaction.Press the working method of example one, adopt the interruption method or add the uninterrupted dual mode of material midway and produce atmospheric cracking silicon rubber and other organosilicon superpolymer as a trial.Its result such as table one.
Table a pair of pipe reactor The pilot plant result
| Numbering | (kg) feeds intake | Product | Once through yield (%) | Electric heating unit consumption kw/kg (oil) | Remarks | ||
| Silicon rubber | Other sand part | Catalyst | |||||
| 1 | 50 | 25 | 6％ | 40 | 53 | 2.5 | The interruption method |
| 2 | 150 | 50 | 6％ | 96 | 48 | 2.4 | Add the material method |
Example three: multitubular reactor suitability for industrialized production
Reactor is zoomed into industrial scale again.Make a multitubular reactor, its useful volume reaches 1000 liters.Reactor head is provided with charging opening, is provided with the material stirring rod in material bed.The partition zone of heating is divided into three heating zones, and is controlled on 150～500 ℃ of each different temperature of reaction sections.Whole reactor and washing, pulverizing, dedusting, condensation, equipment such as separate and form a whole set of complete flow process.As example one operation.Divide first, second, third class Three, the mode of taking every interval to add a defective material in 1～2 hour is produced.Its result such as table two.
The daily output statistics in table two multitubular reactor continuous production three one months of the middle of the month of test manufacture
| Each claims teams and groups | Silicon rubber (kg) | Product (oil) kg | Once through yield (%) | Average electrical thermal power (kw) | Average electric heating unit consumption kw/kg (oil) |
| First class | 248 | 124 | 50.2 | 16.4 | 1.06 |
| Second class | 220 | 120 | 54.5 | 15.4 | 1.03 |
| Third class | 229 | 129 | 56.3 | 14.3 | 0.89 |
| Average daily production | 697 | 373 | 53.5 | 15.4 | 0.99 |
Can predict that overcome the leakage of equipment and shortening, the stable pitch time of adding material, once through yield can reach more than 60%.The material steam that atmospheric cracking forms becomes the thick mixed methylcyclosiloxane of organosilicon through dedusting, condensation separation.Through purifying, making with extra care, quality can reach the quality standard with the direct synthetic organosilicon of silica flour siloxanes to this organosilicon hybrid ring body again.Can be directly used in and make various high-quality organosilicon products.
Processing unit of the present invention is simple, operational safety, yield height, electric heating unit consumption are low.Can make things convenient for, suitability for industrialized production economically.Be the comprehensive utilization of waste silicone rubber, suitability for industrialized production organosilicon ring body has been opened up a new field.
Claims (4)
1, a kind of manufacture method for preparing the organosilicon ring body with silicon rubber, it is characterized in that: selecting waste silicone rubber for use is raw material, comprise sulfuration or not sulfuration, contain filler or do not contain the waste silicone rubber of filler, through washing drain, pulverizing and catalyst pack into after all mixing in the scission reaction stove, atmospheric cracking becomes the organosilicon ring body under 150 ℃～500 ℃ reaction conditions.
2, the described catalyst of claim 1 is alkali metal hydroxide or its aqueous solution, and concentration is 28～35%, and the consumption of catalyst is 3～8% of a raw material weight, and is added with tensio-active agent, and its consumption is 0.2～1.2% of a catalyst.
3, scission reaction stove according to claim 1 adopts the blank pipe vertical structure, and the pipe number of reactor can be single tube or multitube, and the height of pipe is 1～2m, and useful volume is at 0.8m
3More than, the material stirring rod is housed in the pipe, adopt the tube exterior subsection heating, can be 2～3 heating zones, the temperature of each heating zone raises from top to bottom piecemeal.
4, the organosilicon ring body prepared of method according to claim 1 is cyclic methylsiloxane mixture, wherein hexamethyl cyclotrisiloxane (D
3) content be more than 30%, Octamethylcyclotetrasiloxane (D
4) content be more than 40%, hexamethyl cyclotrisiloxane-tetradecamethylcycloheptasiloxane, i.e. D
3-D
7Total content reach 90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92112510 CN1041828C (en) | 1992-11-05 | 1992-11-05 | Organosilicon cyclic body prepared by silastic atmospheric cracking |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92112510 CN1041828C (en) | 1992-11-05 | 1992-11-05 | Organosilicon cyclic body prepared by silastic atmospheric cracking |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1086518A true CN1086518A (en) | 1994-05-11 |
| CN1041828C CN1041828C (en) | 1999-01-27 |
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ID=4945977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92112510 Expired - Fee Related CN1041828C (en) | 1992-11-05 | 1992-11-05 | Organosilicon cyclic body prepared by silastic atmospheric cracking |
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| Country | Link |
|---|---|
| CN (1) | CN1041828C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6262289B1 (en) | 1997-06-11 | 2001-07-17 | Kaneka Corporation | Process for preparing cyclic oligosiloxanes |
| CN1111560C (en) * | 1999-11-09 | 2003-06-18 | 陈彦霖 | A kind of method that from the silicon rubber waste product, reclaims silicon monomer |
| CN103626796A (en) * | 2012-08-28 | 2014-03-12 | 杨晓林 | Recovery method of silicone rubber |
-
1992
- 1992-11-05 CN CN 92112510 patent/CN1041828C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6262289B1 (en) | 1997-06-11 | 2001-07-17 | Kaneka Corporation | Process for preparing cyclic oligosiloxanes |
| CN1111560C (en) * | 1999-11-09 | 2003-06-18 | 陈彦霖 | A kind of method that from the silicon rubber waste product, reclaims silicon monomer |
| CN103626796A (en) * | 2012-08-28 | 2014-03-12 | 杨晓林 | Recovery method of silicone rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1041828C (en) | 1999-01-27 |
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Free format text: CORRECT: INVENTOR; FROM: CHEN ZHENGQI; WENG SUHUA TO: CHEN ZHENGQI |
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Address after: 228 361004, four, 401, Hubin South Road, Fujian, Xiamen Inventor after: Chen Zhengqi Patentee after: Chen Zhengqi Address before: 100073, 19 West Third Ring Road, 93, 5, two, gate, No. Beijing Inventor before: Chen Zhengqi Patentee before: Weng Suhua Inventor before: Weng Suhua Patentee before: Chen Zhengqi |
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