CN101376639B - Method for coproduction of dispersants MF and sodium sulphite - Google Patents

Abstract

The invention discloses a method for preparing dispersant MF in combination with sodium sulfite. The method comprises the following steps: adding more than 95% of sulfuric acid to the methylnaphthalene raw material, charging sulfur trioxide to carry out sulfonation reaction thoroughly, heating, evacuating, and continuously reacting to reach the total acidity of the solution of 22-27%; absorbing sulfur dioxide gas generated by sulfonation reaction with alkali liquor for preparing sodium sulfite; and regulating condensation acidity to 14% to 20% with water, adding formaldehyde aqueous solution for condensation, diluting, and regulating pH to 7 with alkali to obtain dispersant MF. In the method, lime is not required to neutralize so that solid waste such as calcium sulfate can not be generated and the dispersant MF reaches Chinese quality standard GB9294-88. Meanwhile, sulfur oxide waste gas is reasonably reutilized, with the characteristic of low energy consumption; and is a clean environment friendly production process.

Description

A kind of method of producing Dispersant MF and coproduction S-WAT

Technical field

The present invention relates to a kind of preparation method of sulfonated dispersants, specifically be meant a kind of production Dispersant MF, the method for the S-WAT of coproduction simultaneously.

Background technology

Dispersant MF is dispersed dye and the most frequently used a kind of dye dispersant of vat dyes in the world, because it has good dispersion effect, and cheap and doubly be popular.

The common production technique of Dispersant MF be with technical methylnaphthalene (methylnaphthalene content is more than 60%) or washing oil (methylnaphthalene content is more than 25%) through with the vitriol oil carry out sulfonation, again with the formalin condensation, then with lime its residual sulfuric acid that neutralizes, by sodium hydroxide system alkali, filter out solid waste such as calcium sulfate then, obtain the aqueous solution of condensation compound of methyl naphthalene sulfonic acid and formaldehyde, i.e. Dispersant MF.

Existing technology usually with about 98% the vitriol oil as sulphonating agent, its shortcoming is to produce a large amount of remaining spent acid, thereby need neutralize with lime, produces solid waste such as calcium sulfate, the meeting of sulfonation simultaneously produces a large amount of sulfurous gas, thereby influences environment.

Publication number be the Chinese invention patent of CN1081451 by making sulphonating agent with the vitriol oil, come sulfonation with organic solvent (be generally benzene class substituent, as benzene, toluene etc.) azeotropic, utilize the recycle stock of condensation reaction to regulate the laggard capable condensation of its condensation acidity then.This method need be regulated acidity with recycle stock, and will reclaim organic solvent, and technology is complicated, and organic solvent is not complete inertia, can consume a certain amount of sulphonating agent, generates a certain amount of harmful side product, is difficult to separate, thereby influences quality product.Publication number is that the Chinese invention patent of CN1043637 is by making solvent with sulfurous gas, with SO 3 sulfonated, by reclaiming solvent sulfurous gas, remove residual sulfurous gas with nitrogen then, this technology will be evaporated recovery sulfurous gas, sulfurous gas needs cooling simultaneously, need to consume big energy, have more remaining sulfur dioxide in the sulfonated products simultaneously, influence product quality and environment, facility investment is big, and cost is higher.

Summary of the invention

The invention provides a kind of method that adopts new process for sulfonation to produce Dispersant MF, this method technology is simple, free from environmental pollution, is producing simultaneously all right coproduction S-WAT, utilization of resources maximization.

A kind of method of producing Dispersant MF and coproduction S-WAT comprises, adds the sulfuric acid of concentration more than 95% in the methylnaphthalene raw material, feeds sulphur trioxide and carries out sulfonation reaction, and the sulfonation reaction temperature is 30～155 ℃, and optimum is 50～100 ℃; After sulphur trioxide fully reacted, 135～155 ℃ vacuumized, and it is optimum continuing to react to the total acidity 22%～27%, 23%～25% of reaction system; The sulfur dioxide gas body and function alkali lye that sulfonation reaction produces absorbs the preparation S-WAT; Solution after the sulfonation reaction adds water and regulates condensation acidity to 14%～20%, and optimum is 16%～18%, adds formalin and carries out condensation, and the temperature of condensation reaction is generally at 80-120 ℃, and pressure generally is no more than 0.2Mpa; Thin up after condensation finishes adds alkali and regulates the pH value to neutral, obtains the aqueous solution of condensation compound of methyl naphthalene sulfonic acid and formaldehyde, i.e. Dispersant MF.

The principal reaction formula of producing Dispersant MF is as follows:

(1) sulfonation

(2) condensation:

(3) neutralization:

Described methylnaphthalene raw material can adopt pure methylnaphthalene, but for reducing production costs optimum technical methylnaphthalene or the washing oil of adopting.The methylnaphthalene content of described technical methylnaphthalene is more than 60%, and the described methylnaphthalene content of washing oil that gets is more than 25%.When adopting technical methylnaphthalene, the weight ratio technical methylnaphthalene of each material in the reaction: sulfuric acid: sulphur trioxide: formaldehyde=1:0.3～0.45:0.3～0.45:0.12～0.24, preferred technical methylnaphthalene: sulfuric acid: sulphur trioxide: formaldehyde=1:0.35～0.40:0.35～0.40:0.15～0.20; When adopting washing oil, the weight ratio washing oil of each material in the reaction: sulfuric acid: sulphur trioxide: formaldehyde=0.9:0.3～0.45:0.3～0.45:0.12～0.24, preferred washing oil: sulfuric acid: sulphur trioxide: formaldehyde=0.9:0.35～0.40:0.35～0.40:0.15～0.20.

In the reaction process of the inventive method, the methylnaphthalene and the vitriol oil, sulphur trioxide for the first time sulfonation reaction fully after, the rising sulfonation temperature, simultaneously by vacuumizing dehydration, the vitriol oil is reacted comparatively fully, after reaction finishes, only deposit the sulfuric acid of minute quantity in the solution.

The sulfur dioxide gas that sulfonation produces absorbs to pH value 4～9 by alkali lye, and optimum is 5～7, and then adds alkali adjusting pH value to 11～13, and refilter removal of impurities this moment, and the S-WAT content that evaporation concentration, drying obtain can be more than 96%.

Described alkali lye and alkali are optimum to use sodium hydroxide, though also can use yellow soda ash, sodium bicarbonate etc., can produce the greenhouse gases carbonic acid gas in the reaction process.

Compare with common process, technology of the present invention does not need to adopt lime to neutralize, therefore can not produce solid waste such as calcium sulfate, has the low advantage of calcium ions and magnesium ions content simultaneously, because residual free sulfuric acid is less, so the content of sodium sulfate is generally below 5%, quality can reach Chinese quality standard GB9294-88.Simultaneously, form waste gas of sulfur dioxide has also obtained rational recycling, turns waste into wealth, and has characteristic of low energy consumption, is the clean environment firendly production technique.

Embodiment

Embodiment 1

The 60g technical methylnaphthalene is dropped in the reaction vessel, the vitriol oil 23g of adding 98% stirs, and slowly feeds the about 25g of sulfur trioxide gas then, control reaction temperature is at 50～60 ℃, the feeding time was controlled at 1～2 hour, logical finishing, and insulation reaction is after 1 hour, be warming up to 150 ℃, vacuumize, control vacuum tightness is about 0.025Mpa, and reaction is 3 hours under this temperature, sampling and measuring acid number then, after acidity is qualified, cool to 110 ℃, add a certain amount of water, regulate condensation acidity to 18%, cool to 70 ℃ then and add 27g formalin (general concentration is 36%～38%), be warmed up to 110 ℃ of compressive reactions 5 hours, then decrease temperature and pressure, thin up, hydro-oxidation sodium adjust pH promptly gets the aqueous solution of Dispersant MF to neutral, dry pressed powder MF.

Sulfur dioxide gas body and function 15% sodium hydroxide solution that sulfonation produces absorb to pH value be 5.5, it is 13 that adding sodium hydroxide makes the alkali lye pH value after the absorption, filtering and impurity removing, evaporation concentration obtains content and is the commodity S-WAT more than 96% after the drying.

Embodiment 2

The 60g washing oil is dropped in the reaction vessel, the vitriol oil 24g of adding 98% stirs, and slowly feeds the about 26g of sulfur trioxide gas then, control reaction temperature is at 70～80 ℃, the feeding time was controlled at 2～3 hours, and is logical complete, insulation reaction 1 hour, begin to be warming up to 140 ℃, vacuumize, control vacuum tightness is about 0.02Mpa, and reaction is 3 hours under this temperature, sampling and measuring acid number then, after acidity is qualified, cool to 100 ℃, add a certain amount of water, regulate condensation acidity to 20%, cool to 70 ℃ then and add 26g formalin (general concentration is 36%～38%), be warmed up to 110 ℃ of compressive reactions 5 hours, then decrease temperature and pressure, thin up, hydro-oxidation sodium adjust pH promptly gets the aqueous solution of Dispersant MF to neutral, dry pressed powder MF.

Sulfur dioxide gas body and function 15% sodium hydroxide solution that sulfonation produces absorb to pH value be 7, it is 11 that adding sodium hydroxide makes the alkali lye pH value after the absorption, filtering and impurity removing, evaporation concentration obtains content and is the commodity S-WAT more than 96% after the drying.

Embodiment 3

The 60g technical methylnaphthalene is dropped in the reaction vessel, the vitriol oil 24g of adding 98% stirs, and slowly feeds the about 24g of sulfur trioxide gas then, control reaction temperature is at 80～90 ℃, the feeding time was controlled at 2～3 hours, and is logical complete, insulation reaction 1 hour, begin to be warming up to 145 ℃, vacuumize, control vacuum tightness is about 0.03Mpa, and reaction is 3 hours under this temperature, sampling and measuring acid number then, after acidity is qualified, cool to 110 ℃, add a certain amount of water, regulate condensation acidity to 15%, cool to 70 ℃ then and add 28g formalin (general concentration is 36%～38%), be warmed up to 110 ℃ of compressive reactions 5 hours, then decrease temperature and pressure, thin up, hydro-oxidation sodium adjust pH promptly gets the aqueous solution of Dispersant MF to neutral, dry pressed powder MF.

Sulfur dioxide gas body and function 15% sodium hydroxide solution that sulfonation produces absorb to pH value be 7.5, it is 12 that adding sodium hydroxide makes the alkali lye pH value after the absorption, filtering and impurity removing, evaporation concentration obtains content and is the commodity S-WAT more than 96% after the drying.

Claims (3)

1. method of producing Dispersant MF and coproduction S-WAT, comprise, in the methylnaphthalene raw material, add the sulfuric acid of concentration more than 98%, feed sulphur trioxide, 50～100 ℃ are carried out sulfonation reaction, after sulphur trioxide fully reacted, 135～155 ℃ vacuumized, continue to react to the total acidity of reaction system be 23%～25%; The sulfur dioxide gas body and function alkali lye that sulfonation reaction produces absorbs the preparation S-WAT; After solution after the sulfonation reaction adds water and is adjusted to condensation acidity 16%～18%, add formalin and carry out condensation, the condensation back thin up that finishes adds alkali and regulates pH value to neutrality, obtains Dispersant MF; Wherein said methylnaphthalene raw material is technical methylnaphthalene or washing oil, when described methylnaphthalene raw material is technical methylnaphthalene, the weight ratio technical methylnaphthalene of each material in the reaction: sulfuric acid: sulphur trioxide: formaldehyde=1: 0.35～0.40: 0.35～0.40: 0.15～0.20; When described methylnaphthalene raw material is washing oil, the weight ratio washing oil of each material in the reaction: sulfuric acid: sulphur trioxide: formaldehyde=0.9: 0.35～0.40: 0.35～0.40: 0.15～0.20.

2. the method for claim 1 is characterized in that: described sulfurous gas with alkali lye absorb to the pH value be 4～9 o'clock, add alkali and regulate pH value to 11～13, filtering and impurity removing then, evaporation concentration, drying obtains S-WAT.

3. method as claimed in claim 1 or 2 is characterized in that: described alkali lye is sodium hydroxide solution; Described alkali is sodium hydroxide.