CN102070127A

CN102070127A - Method for producing insoluble sulfur

Info

Publication number: CN102070127A
Application number: CN 201110039618
Authority: CN
Inventors: 何蕴琳; 攸路军
Original assignee: SICHUAN CHENHUI CHEMICAL CO Ltd
Current assignee: CITIC Sichuan Huacheng Chemical Co. Ltd.
Priority date: 2011-02-17
Filing date: 2011-02-17
Publication date: 2011-05-25
Anticipated expiration: 2031-02-17
Also published as: CN102070127B

Abstract

The invention discloses a method for producing insoluble sulfur, and belongs to the field of inorganic fine chemical engineering. The production method comprises the following steps of: (1) melting and polymerization; (2) atomization and cold quenching (3) solidification; (4) centrifugal separation; (5) continuous drying; and (6) crushing, screening and charging oil to obtain a finished product. The method is a continuous production method; by the method, the yield of the product is improved; and the product has high purity and stable quality.

Description

A kind of Manufacture of insoluble sulphur method

Technical field

The present invention relates to a kind of producing and manufacturing technique, particularly a kind of Manufacture of insoluble sulphur method.

Background technology

Insoluble sulfur claims polymerised sulphur again, it is to make, gain the name because of being insoluble to dithiocarbonic anhydride through common sulphur thermopolymerization, number of sulfur atoms on its molecular chain is up to more than 108, the visco-elasticity and the molecular weight difference of superpolymer are arranged, and it is widely used in the manufacturing of tire and other rubber combined goods mainly as a kind of senior promotor and vulcanizing agent of rubber industry.

At present, produce insoluble sulfur and be mainly two kinds of methods, be i.e. high-temperature gasification method and watery fusion method.Evaporating method is owing to be at high temperature to carry out polyreaction, so have the high advantage of insoluble sulfur once through yield, but evaporating method gasifies under very high temperature (more than 700 ℃) all usually, and needs very big volume space, so to the equipment requirements height, equipment is at high temperature perishable.The watery fusion method is carried out cold collection behind polymerization reaction take place under the lower temperature, this method makes transformation efficiency low because temperature is low, and the low and poor stability of product purity is adopted when using water as quenching medium, can produce a large amount of waste water, is unfavorable for environmental protection.The patent No. is that the Chinese patent of 03133587.X discloses the method that a kind of watery fusion-gas cooling prepares insoluble sulfur, but this method can expend the gas that is used for quenching in a large number, energy consumption is big, its essence also is a kind of production method of indirect method, its subsequent disposal also needs complicated procedures of forming such as pulverizing, purification, drying, pulverizing, screening, quality product can not reach higher level, and its thermotolerance is relatively poor, and the product fusing point is lower.

Summary of the invention

Goal of the invention of the present invention is: at the problem of above-mentioned existence, provide that a kind of energy consumption is low, yield is high, stay-in-grade insoluble sulfur production method.

The technical solution used in the present invention is such: a kind of Manufacture of insoluble sulphur method comprises the steps:

(1) melt polymerization: solid sulfur is molten into molten sulfur; Pressure-pot internal heating to 380 ℃-440 ℃, and in pressure-pot, fill N ₂Be forced into 0.8-1.2MPa, then at one group of internally heated type collection case internal heating to 580-690 ℃, make sulphur generation polymerization;

(2) the cold collection that atomizes: the high temperature molten sulfur after the polymerization enters under pressure that the pressure type shower nozzle atomizes and cold collection, and cold collection agent is the CS that contains stablizer ₂, tangentially enter and high speed rotating, with the sulfur granules condensation and form uniform particle diameter and be scattered in the extraction liquid;

(3) solidify: mixed emulsion enters in the tower collector of belt stirrer, and soluble sulfur is dissolved, and insoluble sulfur solidifies in device, and solidification value 45-70 ℃, 40-90 minute set time;

(4) centrifugation: the mixture that curing is finished enters the continuous horizontal type whizzer to be separated, and contains the CS of soluble sulfur ₂Recycle after the sent for regeneration;

(5) drying: the insoluble sulfur after the centrifugation enters the CS of continous way helicoid screw dryer the 50-65 ℃ of dry absorption of following indirect heating ₂, obtain the work in-process of content more than 97%.

(6) pulverizing, screening, oil-filled: work in-process through oil-filled, pulverize, be packed as finished product after the screening.

As preferably: stablizer is organic acid salt, alkene or halogen described in (2) step.

The principal feature of present method is: behind the comparatively high temps melt polymerization, be propulsion source with the nitrogen that charges into, utilize the pressure of self, under the effect of shower nozzle, molten sulfur directly atomizes, and forms the fine granularity polymerised sulphur, cold then collection and other subsequent disposal.Present method has been gathered the advantage of high-temperature gasification method and scorification; overcome shortcoming separately simultaneously; charge into nitrogen in present method; its main application is in anaerobic state, prevents that it from oxidizing reaction taking place for protection sulphur; for the molten sulfur atomizing provides necessary pressure support, make the vaporific small-particle of formation more even simultaneously.

In sum, owing to adopted technique scheme, the invention has the beneficial effects as follows:

1, compare with evaporating method, owing to do not need gasification, can energy efficient 36% or more (spending with temperature of reaction 600 is example);

2, compare with evaporating method, can improve yield, evaporating method is because the particle diameter that forms too little (have more than 80% particle diameter less than 5 microns), easily collecting not, the yield of (direct method) is about 40% aborning, and the particle diameter that present method atomizing back forms is bigger, be the 20-150 micron, be convenient to collect, its yield is greater than 60%, (yield is the ratio of raw material sulphur with the insoluble sulphur of product);

3, compare with traditional watery fusion method, because producing, the watery fusion method forms block insoluble sulphur, cause the instability of quality product, also bring many difficulties to subsequent handling, can not serialization production, and present method obtains the uniform relatively insoluble sulfur granules of particle diameter, steady quality also is convenient to postorder and is handled, and can realize serialization production, improved production efficiency, table 1 be existing market product and with the correlation data of the stability of inventive method products obtained therefrom:

In the table, heat stable value is the ratio of the insoluble sulfur content after heating with the preceding insoluble sulfur of heating.The result shows, the quality stability height of present method products obtained therefrom.

Description of drawings

Fig. 1 is a process flow sheet of the present invention.

Embodiment

Below in conjunction with accompanying drawing, the present invention is done detailed explanation.

In order to make purpose of the present invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with drawings and Examples.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.

Embodiment 1:

As shown in Figure 1, solid sulfur is in the fusion of sulfur melting groove internal heating, and temperature is 130 ℃, carries out first section heating through the molten sulfur after the fusion in plunger metering pump with the flow pump-in pressure of 100kg/h is the pressure-pot of heating of 1MPa, and heats continuously to 420 ℃, at N ₂Under the pressure, molten sulfur enters internally heated type collection case continuously, and internally heated type collection case is made up of the pipeline section of 8 closed at both ends, and the interpolation electrothermal tube had both guaranteed safety, and thermo-efficiency is also higher, and the temperature inside the box is 650 ℃, and pressure is 1.2MPa; Under self pressure, molten sulfur enters the pressure type atomizer and atomizes, the molten sulfur after the atomizing and the CS of high speed rotating ₂Mix cold collection, mixed emulsion enters tower collector, and the multilayer agitator is housed in the tower collector, so that thorough mixing makes soluble sulfur obtain dissolving, keeps 60 ℃ of temperature, 70 minutes residence time in the tower collector; The mixed solution that has solidified high speed rotating in the continuous horizontal type whizzer separates; After the centrifugation, contain the CS of solubility sulphur ₂Mother liquor recycles after sending into regeneration system rapidly distillation regeneration, and the insoluble sulphur of solid carries out the indirect heating drying in spiral continuous oven, and 65 ℃ of drying temperatures, dry heat medium are 80 ℃ of hot water; The dried insoluble sulfur of xeromenia obtains finished product through pulverizing, screening, after oil-filled, and product yield is 65.2%.

Embodiment 2:

As shown in Figure 1, solid sulfur is in the fusion of sulfur melting groove internal heating, and temperature is 150 ℃, carries out first section heating through the molten sulfur after the fusion in plunger metering pump with the flow pump-in pressure of 100kg/h is the pressure-pot of heating of 1MPa, and heats continuously to 430 ℃, at N ₂Under the pressure, molten sulfur enters internally heated type collection case continuously, and internally heated type collection case is made up of the pipeline section of 12 closed at both ends, and the interpolation electrothermal tube had both guaranteed safety, and thermo-efficiency is also higher, and the temperature inside the box is 580 ℃, and pressure is 0.8MPa; Under self pressure, molten sulfur enters the pressure type atomizer and atomizes, the molten sulfur after the atomizing and the CS of high speed rotating ₂Mix cold collection, mixed emulsion enters tower collector, and the multilayer agitator is housed in the tower collector, so that thorough mixing makes soluble sulfur obtain dissolving, keeps 45 ℃ of temperature, 90 minutes residence time in the tower collector; The mixed solution that has solidified high speed rotating in the continuous horizontal type whizzer separates; After the centrifugation, contain the CS of solubility sulphur ₂Mother liquor recycles after sending into regeneration system rapidly distillation regeneration, and the insoluble sulphur of solid carries out the indirect heating drying in spiral continuous oven, and 50 ℃ of drying temperatures, dry heat medium are 80 ℃ of hot water; The dried insoluble sulfur of xeromenia obtains finished product through pulverizing, screening, after oil-filled, and product yield is 62.8%.

Claims

1. a Manufacture of insoluble sulphur method is characterized in that comprising the steps:

(5) drying: the insoluble sulfur after the centrifugation enters the CS of continous way helicoid screw dryer the 50-65 ℃ of dry absorption of following indirect heating ₂, obtain the work in-process of content more than 97%;

2. Manufacture of insoluble sulphur method according to claim 1 is characterized in that: stablizer is organic acid salt, alkene or halogen described in (2) step.