CN1045432C - Preparation technology and equipment for sodium salt of methyl propenyl sulfonic acid - Google Patents

Abstract

The present invention provides a technology for manufacturing sodium methyl allyl sulfonate (SMAS) and devices. The technology takes methylpropene chlorine and sodium sulfite as raw materials, and adopts a mother liquid circulating method for manufacturing the SMAS. Producing technology is divided into four processes: (1), an activated carbon absorbing and filtering process for shedding water in the front period of a reaction; (2), an evaporative dehydration, thermo filtration for desalination and crystallization process; (3), a centrifugal separation, product washing and refining and mother liquid circulating process; (4), a humidity product drying process. Because the mother liquid circulating method is adopted by the present invention, finished product yield reaches 91.6%, which greatly improves the finished product yield of products.

Description

Sodium methallyl sulfonate production method and equipment

The present invention relates to the organic chemistry acyclic compound, be meant that especially a kind of is producing and manufacturing technique and the equipment thereof that raw material adopts Recycling Mother Solution legal system sodium methallyl sulfonate with methylallyl chloride and sodium sulphite anhydrous 99.3.

Sodium methallyl sulfonate (hereinafter to be referred as SMAS) is improved the dyeing behavior of acrylic fibers mainly as the 3rd monomer of making acrylic fibers, has advantages such as Heat stability is good, dyeability are good.At present, domestic still do not have other manufacturer production.Mainly adopt solvent extration and produce SMAS abroad, this processing method needs evaporating water, and needs elevated temperature heat to filter, operational difficulty, equipment requirements height, also need consume the higher organic solvent of a large amount of value, the finished product yield is lower, thereby has limited the further popularization of this technology.

Purpose of the present invention just is to overcome existing SMAS production technique defective, provides a kind of by methylallyl chloride is dropped in the sodium sulfite solution continuously, adopts the new production technique of Recycling Mother Solution legal system SMAS.

SMAS production technique of the present invention is a raw material with methylallyl chloride and sodium sulphite anhydrous 99.3, adopts Recycling Mother Solution legal system SMAS;＜1〉by glassed steel reaction vessels methylallyl chloride is dropped to continuously and make thick SMAS in the sodium sulfite solution, and dealkylation reaction water in early stage, reaction solution removes the impurity iron ion through charcoal absorption then;＜2〉remove portion water in the reaction solution through dehydration by evaporation, remove most of solid sodium chloride that dehydration by evaporation is separated out through heat filtering again, by cool, crystallization separates out the SMAS major part;＜3〉this subsequently solidliquid mixture enters whizzer, Recycling Mother Solution after centrifugal is returned the absorption still and is carried out charcoal absorption, again repeating step＜2 〉,＜3, and crystallization kettle is returned in washings circulation for the first time in the centrifugal process, carry out crystallization and centrifugal again, to improve the finished product yield;＜4〉send into drying machine through the solid materials that washs after centrifugal, SMAS gets product after the drying.The main chemical reactions formula of technology of the present invention is as follows:

SMAS production technique of the present invention is divided into four processes:＜1〉reaction, dealkylation reaction early stage water, charcoal absorption and filtration procedure;＜2〉dehydration by evaporation, heat filtering desalination and crystallisation process;＜3〉centrifugation, the refining and Recycling Mother Solution process of product washing;＜4〉wet product drying process.In process of production, the centrifuge mother liquor circulation is returned the absorption still and is carried out charcoal absorption and filtration again, and then makes with extra care and the Recycling Mother Solution process through dehydration by evaporation, heat filtering desalination and crystallisation process and centrifugation, product washing; Centrifuge mother liquor after repeatedly circulating also is used for washing the salt slag that heat filtering leaches; And in the centrifugal process for the first time washings also circulate and return crystallization kettle, carry out crystallization and centrifugal again, the SMAS that is taken out of with abundant recovery centrifuge mother liquor, salt slag and centrifuge washing liquid.The main control parameters of this production process is as follows:

Sequence number controlled variable title index

1 raw material specification methylallyl cl content 〉=97.0% (wt%)

Sodium sulphite anhydrous 99.3 content 〉=96.0% (wt%)

2 proportioning methylallyl chlorides: sodium sulphite anhydrous 99.3 0.7-1.5: 1 (mol)

3 methylallyl chlorides drip time 0.5-5hr

4 temperature of reaction 20-100 ℃

Pressure-0.10-0.30MPa

Time 0.5-5hr

Take off 20-150 ℃ of water temp in early stage after 5 reactions

Pressure-0.10-0.30MPa

20-100 ℃ of 6 absorption still temperature

Pressure-0.10-0.30MPa

7 evaporator temperature 20-130 ℃

Pressure-0.10-0.30MPa

30-165 ℃ of 8 heat filter temperature

Pressure-0.10-0.30MPa

0-100 ℃ of 9 crystallization kettle temperature

Pressure-0.10-0.30MPa

50-150 ℃ of 10 drying machine temperature

Pressure-0.10-0.30MPa

The finished product SMAS yield that makes through technology of the present invention reaches 91.6% (to the mole yield of methylallyl chloride), and the quality index of SMAS finished product is as follows:

Sequence number index name index

1 appearance white plate crystal

2 purity (wt%) 〉=99.00%

3 sodium chloride contents (wt%)≤0.10%

4 sodium sulphate contents (wt%)≤0.10%

5 S-WAT content (wt%)≤0.05%

6 iron level ppm≤0.4ppm

7 water-insoluble ppm≤50ppm

8 water capacities (wt%)≤0.50%

Advantage of the present invention just is to make the finished product yield reach 91.6% owing to adopted the Recycling Mother Solution method, has improved the finished product yield of product greatly.This technology is compared with solvent extration technology, does not need evaporating water and elevated temperature heat to filter, and technological operation is simple relatively, and this processing unit require low, do not consume organic solvent.Therefore this production technique has fabulous promotional value.

The invention will be further described below in conjunction with accompanying drawing; Fig. 1 is a process flow diagram of the present invention, and Fig. 2 is a technology evaporation structure synoptic diagram of the present invention.

With reference to Fig. 1, the technological process of production of the present invention is by sodium sulfite dissolution kettle 1, methylallyl chloride storage tank 2, methylallyl chloride head tank 3, reactor 4, dump tank 5, absorption still 6, cold filter 7, filtrate tank 8, evaporimeter 9, measuring tank 10, heat filter 11, crystallization kettle 12, centrifuge 13, wash water head tank 14a, b, c, the equipment such as d, mother liquor tank 15, drying machine 16 consist of, R represents to adsorb still 6, N represent to decrystallize still 12, K and represents wash water head tank 14a among the figure, b, c, P represent finished product SMAS.

When producing, the raw material sodium sulfite is delivered in the reactor 4 by delivery pump after the dissolving of sodium sulfite dissolution kettle 1 usefulness pure water, the raw material methylallyl chloride is delivered to methylallyl chloride head tank 3 by methylallyl chloride storage tank 2 through delivery pump, when reaction, opening reactor 4 stirs, drip methylallyl chloride 0.5-5hr by methylallyl chloride head tank 3 to reactor 4, then stop to drip stirring reaction 0.5-5hr, reaction temperature is controlled at 20-100 ℃, and pressure is controlled to be-0.10-0.30MPa. React complete after, temperature be 20-150 ℃, pressure for deviate under-the 0.10-0.30MPa a certain amount of early stage water and the impurity such as unreacted methylallyl chloride enter dump tank 5, send the boiler burning disposal. Reactant liquor autoreaction still 4 enters in the absorption still 6, and the unformed sawdust active carbon that adds 0.5-2% (wt%) load responsive fluid stirs, the control temperature is 20-100 ℃, pressure is-0.10-0.30MPa, then this solution with solid activated carbon is sent in the cold filter 7 and filtered, filtrate flows in the filtrate tank 8, the cake solids active carbon is done burning and is processed, filtrate is delivered in the evaporimeter 9 through delivery pump from filtrate tank 8, the control temperature is 20-130 ℃ in evaporimeter 9, pressure is-0.10-0.30MPa, through dehydration by evaporation, steam the water yield by measuring tank 10 meterings, the water yield varies with temperature the calculating gained by SMAS at the dissolved in filtrate degree, so that SMAS reaches the critical saturation state of this temperature in evaporimeter 9, to separate out most of accessory substance solid sodium chloride in the solution this moment, liquid-solid mixture behind this dehydration by evaporation is sent in the heat filter 11, the control temperature is 30-165 ℃, pressure is-0.10-0.30MPa, carry out heat filtering, the solid salt slag that leaches is after the washing of the centrifuge mother liquor after the Recycling Mother Solution repeatedly, send boiler to process, filtrate is sent in the crystallization kettle 12, the control temperature is 0-100 ℃ in crystallization kettle 12, pressure is-0.10-0.30MPa, carry out crystallisation by cooling, separate out a large amount of solid SMAS, then this solidliquid mixture is entered and carry out centrifugation in the centrifuge 13, centrifugal rear mother liquid obtained sending in the mother liquor tank 15, deliver to circulation production in the absorption still 6 by delivery pump again, to reclaim SMAS wherein, solid-phase product in the centrifuge 13 is removed impurity by-product solid sodium chloride in the product through 14 washings of wash water head tank, the washing order is: centrifugal with carrying out spray washing in the adding of the washing lotion in a groove centrifuge 13 first, gained centrifugate through mother liquor tank 15 by being pumped in the crystallization kettle 12, with the filtrate crystallisation by cooling behind the heat filtering next time. Add with the washing lotion in the b groove that to carry out spray washing in the centrifuge 13 centrifugal, gained centrifugate is sent into a groove through mother liquor tank 15 by delivery pump, uses in order to next centrifuge washing again. Equally, it is centrifugal to carry out spray washing with the washing lotion in the c groove, and the centrifugate of gained is delivered to the b groove through mother liquor tank 15 by delivery pump, and the centrifugate after centrifugal with the washing of the pure water in the d groove is delivered to the c groove through mother liquor tank 15 by delivery pump, supplies pure water at last in the d groove. Solid purified product in the centrifuge 13 after four washings is sent into and is carried out drying in the drying machine 16, and to be 50-150 ℃, pressure be-0.10-0.30 MPa to the control temperature. Namely make finished product SMAS after the drying.

With reference to Fig. 2, evaporimeter is composite construction, and top is vaporizer, liner enamel material; The bottom is tubular heat exchanger, and wherein tubulation adopts titanium material (titanium pipe), is a center circulation pipe in section of tubulation group center, and the specification ratio of center circulation pipe and tubulation diameter is 3-6: 1. Material is heated in tubulation, reaches the vaporization purpose on evaporimeter top. Such as figure, W is that material inlet, M are that to be respectively steam import and export, T1 and T2 be that temperature-measuring port, F1 and F2 are that visor mouth, e are that pressure tap, b, c and d are that for subsequent use mouthful, a is steam outlet for material outlet, S1 and S2.

Below be embodiments of the invention, practical application of the present invention is not limited to embodiment.

Example 1 is that raw material adopts Recycling Mother Solution legal system SMAS with S-WAT and methylallyl chloride.

300 tons/year of throughput

Raw material S-WAT content 〉=96.0% (wt)

Raw material methylallyl cl content 〉=97.0% (wt)

Main equipment specification:

1. 3000 liters of bands of S-WAT dissolution kettle K3000L volume stir glass-lined equipment

2. 5000 liters of glass-lined equipments of methylallyl chloride storage tank TT-K5000L volume

3. 500 liters of glass-lined equipments of methylallyl chloride header tank TT-K500L volume

4. 3000 liters of bands of reactor K3000L volume stir glass-lined equipment

5. receiver φ 600 * 1000 * 6 materials are carbon steel

6. 3000 liters of bands of absorption still K3000L volume stir pool glass equipment

7. on the cold strainer φ 1300 * 1000 not with the glass-lined equipment of end socket

8. 3000 liters of glass-lined equipments of filtrate tank TT-K3000L volume

9. scale tank φ 700 * 3000 materials are 1Cr18Ni9Ti

10. heat filter φ 1200 * 8 materials are lining titanium, (composite titanium)

11. vaporizer φ 1600 * 2400+ φ 1000 * 2000 materials (compound)

12. 5000 liters of bands of crystallization kettle K5000L volume stir glass-lined equipment

13. 4 of 500 liters of glass-lined equipments of wash water header tank TT-K500L volume

14. whizzer WG-1200

15. 3000 liters of glass-lined equipments of mother liquor tank TT-K3000L volume

16. drying machine GZQ3 * 4.5

Take by weighing the 380Kg S-WAT, join in the S-WAT dissolution kettle, add the 1503Kg pure water simultaneously, after the stirring and dissolving, deliver in the reactor with transferpump.322 liters of methylallyl chlorides of metering are delivered in the methylallyl chloride header tank with transferpump in the methylallyl chloride storage tank, open reactor and stir, and begin to drip methylallyl chloride, and controlled temperature is 50-80 ℃, and pressure is 0-0.10MPa, and the dropping time is 1-3hr.After reaction finishes, be 50-80 ℃ in temperature, pressure is for beginning to take off water and impurity such as unreacted methylallyl chloride in early stage under the-0.01-0.1MPa, and the about 156Kg of gained waste liquid enters receiver; The about 2025Kg of gained reaction solution enters the absorption still, add gac 15Kg, add pure water 33Kg simultaneously, controlled temperature is 50-80 ℃, pressure is that 0-0.10MPa stirs down, then this solidliquid mixture being put into cold strainer filters, the 2054Kg filtrate of gained enters filtrate tank, and filtrate is sent in the vaporizer through transferpump, and controlled temperature is 70-100 ℃ in vaporizer, pressure evaporates the water yield and is measured by scale tank for-0.05-0.1MPa, the about 703Kg of dehydration behind the arrival dehydration terminal point, stops dehydration altogether, last about 1351Kg liquid-solid mixture is sent in the heat filter, control heat filter temperature is 50-80 ℃, and pressure is 0-0.30MPa, through heat filtering, can get about 85Kg salt slag, these salt slags must send boiler to handle after the centrifuge mother liquor washing through gained after the Recycling Mother Solution repeatedly.The about 1266Kg filtrate of gained enters crystallization kettle from heat filter, at this controlled temperature is 30-60 ℃, pressure is 0-0.10MPa, crystallisation by cooling, SMAS is separated out, then this liquid-solid mixture is entered in the whizzer, mother liquid obtained entering in the mother liquor tank after the centrifugation, send back in the absorption still with transferpump again, adsorb cold filtration, dehydration by evaporation, wherein product is reclaimed in the centrifugal circulation of heat filtering and crystallization, and two to three later centrifuge mother liquors like this remove to wash the salt slag that leaches again from heat filtering, and the washing lotion of gained loops back the absorption still again.The thick product of solid materials in whizzer washs through the wash water header tank, the washing order is: join in the whizzer with the about 40Kg spray of the washing lotion in a groove earlier, it is centrifugal to enter washing, the centrifugate of gained through mother liquor tank by the filtrate crystallization in the lump after being pumped to crystallization kettle and heat filtering next time, add in the whizzer with the about 40Kg spray of the washing lotion in the b groove again, wash centrifugal, gained centrifugate through mother liquor tank by being pumped into a groove, to make washing washing lotion next time.Equally, spray in the whizzer with the about 40Kg of washing lotion in the C groove, behind the centrifuge washing, gained centrifugate by being pumped to the b groove, is used washing lotion to do to wash next time through mother liquor tank.Spray in the whizzer with about 20Kg pure water in the d groove, gained centrifugate by being pumped to the C groove, to make washing washing lotion next time, at last, in the d of sky groove, is supplied about 20Kg pure water through mother liquor tank behind centrifuge washing, to make washing washing lotion next time.Thick product in the whizzer through four washings of washing lotion after, send into again that drying promptly makes finished product SMAS in the drying machine.

Technology of the present invention can adapt to production requirement, the SMAS steady quality of producing, and the 3rd monomer that is used as the acrylic fiber production process process conforms to quality requirements, and the user is satisfied.

Example 2, various processes method correlation data

Explained hereafter SMAS of the present invention adopts the Recycling Mother Solution method, adopts same raw material system SMAS in the laboratory, but the refining solvent extration that adopts in back, though two kinds of methods, raw material are the same, reacting phase is with, but gained difference as a result, and following table has been listed both testing datas relatively under laboratory condition.

(wherein DMF is a dimethyl formamide)

Project	Method
				Solvent extration	The Recycling Mother Solution method
Sodium sulphite anhydrous 99.3 mol	0.948	0.5
			Methylallyl chloride mol	1.2	0.544
The circulation mother liquor
			Weight g	/	350
SMAS ％	/	18.98
			NaCl ％	/	13.1
H2O ml	260	260
			Emulsifying agent g	2
Steam water yield ml	Evaporate to dryness	253
			Separate out the salt slag
Weight g	/	26.8
			SMAS ％	/	8.019
NaCl ％	/	92.04
			Mother liquor
Weight g	/	321.4
			SMAS ％	/	18.44
NaCl ％	/	13.91
			Mother liquor is condensed into amount of solid g	124	/
The DMF consumption
			Ml for the first time	500	/
Ml for the second time	70	/
			SMAS is separated out in crystallization
Weight g	52.7	73.7
			SMAS ％	96.32	97.7
NaCl ％	2.66	1.576
			Extraction gained SMAS
Weight g	64	/
			SMAS ％	95.93	/
NaCl ％	0.5354	/
			SMAS total yield %	74	91.46

Claims (5)

1, a kind of sodium methallyl sulfonate SMAS production method is a raw material with methylallyl chloride and sodium sulphite anhydrous 99.3, it is characterized in that it adopts Recycling Mother Solution legal system SMAS;

＜1〉by glassed steel reaction vessels methylallyl chloride is dropped to continuously and make thick SMAS in the sodium sulfite solution, and dealkylation reaction water in early stage, reaction solution removes the impurity iron ion through unformed sawdust charcoal absorption then;

＜2〉remove portion water in the reaction solution through dehydration by evaporation, remove most of solid sodium chloride that dehydration by evaporation is separated out through heat filtering again, by cool, crystallization separates out the SMAS major part;

＜3〉this subsequently solidliquid mixture enters whizzer, and the Recycling Mother Solution after centrifugal is returned the absorption still and carried out charcoal absorption, again repeating step＜2 〉,＜3; And crystallization kettle is returned in washings circulation for the first time in the centrifugal process, carries out crystallization and centrifugal again;

＜4〉send into drying machine through the solid materials that washs after centrifugal, SMAS gets product after the drying.

2, SMAS production method according to claim 1, the proportioning that it is characterized in that methylallyl chloride and S-WAT is 0.7-1.5: 1mol, the dropping time is 0.5-5hr to methylallyl chloride continuously, temperature of reaction 20-100 ℃, pressure-0.10-0.30MPa, reaction times 0.5-5hr, 20-130 ℃ of vaporizer controlled temperature, pressure-0.10-0.30MPa.

3, SMAS production method according to claim 1 is characterized in that the centrifuge mother liquor after repeatedly circulating also is used for washing the salt slag that heat filtering leaches.

4, according to the employed vaporizer of the described SMAS production method of claim 1, it is characterized in that its top is vaporizing chamber, liner lass lining material, the bottom is a tubular heat exchange, wherein tubulation adopts the titanium material, is a center circulation tube in portion of tubulation group center.

5, the employed vaporizer of SMAS production method according to claim 4, the ratio that it is characterized in that center circulation tube and tubulation diameter is 3-6: 1.

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