CN101590402A

CN101590402A - The using method of stannous oxide catalyst in the esterification step in production of plasticizer

Info

Publication number: CN101590402A
Application number: CNA2009100205886A
Authority: CN
Inventors: 刘统毅; 刘延华; 刘建军; 孙长春; 崔峰; 张建平
Original assignee: Zibo Bluesail Chemical Co Ltd
Current assignee: Zibo Bluesail Chemical Co Ltd
Priority date: 2009-04-24
Filing date: 2009-04-24
Publication date: 2009-12-02

Abstract

The using method of stannous oxide catalyst in the esterification step in production of plasticizer of the present invention is characterized in that thermal spraying stannous oxide on reactor inwall and inner disc tube wall, and coating thickness is 0.1mm.Heating source heatable catalyst at first when carrying out esterification, thus improve the temperature of catalyst, improve active can, thereby improve reaction speed; Need not in reactor, to add again catalyst in the production process; Can shorten the production cycle, optimize production technology, save production cost.

Description

The using method of stannous oxide catalyst in the esterification step in production of plasticizer

Technical field

The present invention relates to the adding mode of plasticizer industry catalyst for esterification reaction, particularly the using method of stannous oxide catalyst in the esterification.

Background technology

In the technology of at present domestic and international suitability for industrialized production plasticizer, the catalyst that is adopted in esterification step mainly contains: several types such as sulfuric acid, nonacid titanate esters, stannous oxide.

1. use that sulfuric acid is done good catalyst activity, reaction temperature is low, but the seriously corroded to not being equipped with, side reaction is many, and reaction finishes the back also need add alkali neutralization and washing processing for removing sulfuric acid, causes complex manufacturing, and loss of material is many;

2. use nonacid titanate esters to do that catalyst has the catalytic activity height, selectivity is good, side reaction is few, advantage such as etching apparatus and wastewater flow rate be not less relatively, but reaction finishes also need neutralize, washing step is removed the catalyst hydrolysate in the material, and titanium ion can have remnants in material, influence the resistivity of product.

3. use stannous oxide to make catalyst, then comprise two kinds of materials and do said all advantages of catalyst, and do not exist above-mentioned two kinds of materials to do the said problem of catalyst, the technological process of being adopted comprises: esterification step, in and washing step, the stripping drying process filters operation and wastewater treatment operation.Fig. 2 is seen in concrete technological process.This technological process, earlier throw alcohol in proportion and throw acid anhydrides and catalyst again, temperature reaction then, catalyst and material fully mix, after main reaction was finished, catalyst and material entered next operation together, in to the product purification process, the NaOH of catalyst and adding is drained together, causes waste and environmental pollution.In the esterification step, exist the cycle long, conversion ratio is low, cost is high and the subsequent handling complicated problems

4. in certain temperature, activity of such catalysts improves with the rising of temperature.

Summary of the invention

Technical problem to be solved by this invention provides the using method of stannous oxide catalyst in a kind of esterification step in production of plasticizer, can shorten the esterification cycle, and catalyst can reuse, and improves conversion ratio, reduces production costs.

The using method of stannous oxide catalyst in the esterification step in production of plasticizer of the present invention is characterized in that thermal spraying stannous oxide on reactor inwall and inner disc tube wall, and coating thickness is 0.1mm.

Esterification reaction temperature is 220 ℃-240 ℃.

Stannous oxide, chemical formula SnO, molecular weight 134.7, dull gray or brown-black powder, water insoluble and pure, when using, do not participate in reaction as catalyst, quality and character do not change before and after reaction; Belong to metal oxide, can adopt the method for thermal spraying, its spraying is fixed on reactor inwall and the inner disc tube wall.Heat spraying method has oxyacetylene torch spraying, detonation flame spraying, HVOF, electric arc spraying, plasma spraying, low-voltage plasma spraying, the steady plasma spraying of water etc., in order to prevent in spraying process, the oxidation of stannous oxide, the method applied in the present invention are preferably HVOF or plasma spraying (known technology).Main Construction Plan is as follows:

1. the pressure of fetching water is found out the leak source of inner disc tube wall, and pressure will be higher than actual working pressure;

2. adopt the weldering of argon fox that leakage position is carried out repair welding and handle, quality of materials will be higher than bulk material;

3. butt welding point is carried out grinding process;

4. machinery is blown sand, and reaches the Sa3 level, i.e. the most thorough cleaning level in the bottom layer treatment standard;

5. with bottoming special metals powder material spray coating, with the bond strength of guaranteeing coating and housing construction greater than 50MPa;

6. use stannous oxide spray work coating, thickness is 0.1 millimeter;

7. coating type sealing of hole is handled.

Catalyst is sprayed on device interior on heating source, heating means, can outer wall heating, also can the inwall heating, heat source temperature＜420 ℃.Main raw material charge ratio is constant, after acid anhydrides and alcohol are thrown in the equipment, under the effect that is sprayed on the catalyst on the reactor wall, material is participated in reaction, after reaction is qualified, pour material into next refining step, catalyst is stayed in the reactor, continues to feed intake and carries out the reaction of next still again, need not to add catalyst, reduced the processing catalyst process of back system, product quality improves.Carry out the improved technological process of the present invention as shown in Figure 1.

Use the inventive method that following advantage is arranged:

When 1. heating, heating source is heatable catalyst at first, makes the catalyst temperature raising speed up, and catalyst activity strengthens, and has shortened the esterification cycle.

2. the catalyst that is sprayed on reactor inwall and the inner disc tube wall can reuse, and when carrying out esterification, need not to add catalyst in reactor, the conservation cost again.The addition of normal catalytic agent is 0.02 (wt) % of material, and when spraying, coating thickness is 0.1 millimeter, according to 20m ³Reactor to calculate quantity for spray be 4.5kg, can reuse 600 times.Calculate according to every still 2kg that normally feeds intake, 600 stills * 2kg=1200kg, per kilogram is equivalent to 300,000 RMB according to 250 yuan of calculating, spray 4.5 kilograms, closes 1125 yuan, and spraying take 30000 yuan, and 31125 yuan altogether, saving 300000-31125=268875 unit.

3. the enhancing of catalyst activity can make very thorough that esterification carries out, and the conversion ratio of acid anhydrides has reduced the unit consumption of raw material near 100%.

4. shorten the esterification cycle, make that same steam consumption quantity can the production more products, reduced the unit consumption of public work.

5. catalyst is fixed on the tube wall, has avoided the remnants of catalyst in the material, has improved the quality of product.

6. greatly reduce the acid number of esterification, during the material after making esterification qualified can carry out and washing step directly enter the stripping dealcoholysis, thereby complicated step is oversimplified, saved investment at this auxiliary material of NaOH.

7. in the whole process flow, also reduce the technique waste water amount of water consumption, water content and the device generation of product in having cut with washing step, reduced production cost.

Be applicable to that the plasticizer that the present invention produces has: dioctyl phthalate (DOP), diisooctyl phthalate (DIOP), dinonyl phthalate (DNP), diisononyl phthalate (DINP), phthalic acid two (2-ethyl fourth) ester (DIHP), dibutyl phthalate (DHP) (DHP), didecyl phthalate (DOP), phthalic acid is just hot. positive ester in the last of the ten Heavenly stems (810 ester), O-phthalic is misery. 13 esters, DOTP (DOTP), sebacate dioctyl ester (DOS), dioctyl adipate (DOA), diisononyl adipate (DINA), diisooctyl adipate (DIOA), triisooctyl trimellitate (TOTM) etc.

Be applicable to that the present invention comes the esterification raw material of suitability for industrialized production plasticizer to be: phthalic acid, trimellitic anhydride, terephthalic acid (TPA), adipic acid, decanedioic acid, glutaric acid; The esterification raw alcohol is: n-octyl alcohol, isooctanol, n-heptanol, iso-heptanol, Decanol, isodecanol, n-nonyl alcohol, isononyl alcohol etc.

Description of drawings

Fig. 1 is the technological process of production figure of the plasticizer behind employing the present invention;

Fig. 2 is the technological process of production figure of existing plasticizer.

The specific embodiment

By the comparison of Fig. 1, Fig. 2 process chart, as can be seen, stannous oxide catalyst is sprayed on device interior on heating source, main raw material charge ratio is constant, after acid anhydrides and alcohol were thrown in the equipment, under the effect that is sprayed on the catalyst on the reactor wall, material was participated in reaction, after reaction is qualified, pour material into next refining step, catalyst is stayed in the reactor, continues to feed intake and carries out the reaction of next still again, need not to add catalyst, reduced the processing catalyst process of back system.

The addition of traditional handicraft normal catalytic agent is 0.02% of a material, and when spraying, coating thickness is 0.1 millimeter, according to 20m ³Reactor to calculate quantity for spray be 4.5kg, can reuse 600 times.

Embodiment one:

Under reactor condition and all identical situation of raw material proportioning, adopt the inventive method and traditional handicraft to produce the parameter comparison of DOA.

The project of contrast	Traditional handicraft	The inventive method
The project of contrast	Traditional handicraft	The inventive method	The alkyd proportioning	1.5∶1	1.5∶1
The catalyst addition	By 0.02% of inventory	Do not need	The alkyd proportioning	1.5∶1	1.5∶1
The catalyst addition	By 0.02% of inventory	Do not need	Esterification reaction temperature	220-240℃	220-240℃
Reaction time of esterification	5-6h	3-4h	Esterification reaction temperature	220-240℃	220-240℃
Reaction time of esterification	5-6h	3-4h	Feed stock conversion	97％-99％	99.97％
The esterification acid number	0.30mgKOH/g	0.05-0.07mgKOH/g	Feed stock conversion	97％-99％	99.97％
The esterification acid number	0.30mgKOH/g	0.05-0.07mgKOH/g	In and operation	Necessary operation	Do not need
Washing step	Necessary operation	Do not need	In and operation	Necessary operation	Do not need
Washing step	Necessary operation	Do not need	The dealcoholysis operation	Need	Need
Filter operation	Need	Need	The dealcoholysis operation	Need	Need
Filter operation	Need	Need	The waste water operation	Need	Need
Product purity	97％-99％	≥99.5％	The waste water operation	Need	Need
Product purity	97％-99％	≥99.5％	The product water content	0.1％	0.01％
Water consumption	Greatly	Little	The product water content	0.1％	0.01％
Water consumption	Greatly	Little	The sewage generation	Greatly	Little
The public work consumption	Greatly	Little	The sewage generation	Greatly	Little

Embodiment two:

Under reactor condition and all identical situation of raw material proportioning, adopt the inventive method and traditional handicraft to produce the parameter comparison of TOTM.

The project of contrast	Traditional handicraft	The inventive method
The project of contrast	Traditional handicraft	The inventive method	The alkyd proportioning	1.5∶1	1.5∶1
The catalyst addition	By 0.02% of inventory	Do not need	The alkyd proportioning	1.5∶1	1.5∶1
The catalyst addition	By 0.02% of inventory	Do not need	Esterification reaction temperature	220-240℃	220-240℃
Reaction time of esterification	8-10h	5-6h	Esterification reaction temperature	220-240℃	220-240℃
Reaction time of esterification	8-10h	5-6h	Feed stock conversion	97％-99％	99.98％
The esterification acid number	0.30mgKOH/g	0.05-0.07mgKOH/g	Feed stock conversion	97％-99％	99.98％
The esterification acid number	0.30mgKOH/g	0.05-0.07mgKOH/g	In and operation	Necessary operation	Do not need
Washing step	Necessary operation	Do not need	In and operation	Necessary operation	Do not need
Washing step	Necessary operation	Do not need	The dealcoholysis operation	Need	Need
Filter operation	Need	Need	The dealcoholysis operation	Need	Need
Filter operation	Need	Need	The waste water operation	Need	Need
Product purity	97％-99％	≥99.5％	The waste water operation	Need	Need
Product purity	97％-99％	≥99.5％	The product water content	0.1％	0.01％
Product resistivity	0.5×10 ¹⁰	3.0×10 ¹⁰	The product water content	0.1％	0.01％
Product resistivity	0.5×10 ¹⁰	3.0×10 ¹⁰	The sewage generation	Greatly	Little
The public work consumption	Greatly	Little	The sewage generation	Greatly	Little

Claims

1, the using method of stannous oxide catalyst in the esterification step in production of plasticizer is characterized in that thermal spraying stannous oxide on reactor inwall and inner disc tube wall, and coating thickness is 0.1mm.

2, using method according to claim 1 is characterized in that esterification reaction temperature is 220 ℃-240 ℃.

3, using method according to claim 1 and 2, it is just hot to it is characterized in that described esterification is fit to dioctyl phthalate, diisooctyl phthalate, dinonyl phthalate, diisononyl phthalate, phthalic acid two (2-ethyl fourth) ester, dibutyl phthalate (DHP), didecyl phthalate, phthalic acid. and positive last of the ten Heavenly stems, ester, O-phthalic were misery. the production of 13 esters, DOTP, sebacate dioctyl ester, dioctyl adipate, diisononyl adipate, diisooctyl adipate or triisooctyl trimellitate.