CN101875609B - Method for preparing PVC plasticizer from by-products of production of fumaric acid and recovery alcohol - Google Patents

Abstract

The invention relates to a method for preparing a PVC plasticizer by taking by-products of production of fumaric acid and recovery alcohol as raw materials. The method comprises the following steps of: 1, adding 1 part of acid water residues, 2 to 4 parts of recovery isooctanol or recovery isononyl alcohol and 200 to 400ppm of esterification catalyst into a reactor with a thermometer, a distillation and condensing device and a stirring device, and heating the mixture with stirring to the temperature of between 120 and 160 DEG C for yielding water; 2, continuing heating to the highest reaction temperature of 220 DEG C, controlling the temperature of cut fraction to be between 80 and 102 DEG C all the time in the process of a reaction, and reacting until an acid value is less than 1.0 mgKOH/g; and 3, reducing the temperature until the temperature is 190 DEG C or 215 DEG C, performing dealcoholization under the reduced pressure of between -600 and -740 mmHg for 1 to 2 hours, stopping the reaction, and cooling and filtering to obtain a finished product. The method can utilize scrap materials of enterprises effectively, reduce the production cost of the plasticizer and the treatment cost of waste liquor and reduce environmental pollution.

Description

Produce by product and reclaim the pure method for preparing the PVC softening agent with fumaric acid

Technical field

The present invention relates to a kind of method for preparing the PVC softening agent take fumaric acid production by product (sour water slag) and recovery alcohol (isooctyl alcohol or isononyl alcohol) as raw material.

Background technology

There is at present research to use the reported in literature of fumaric acid and the synthetic softening agent diisooctyl fumarate of isooctyl alcohol.The research hydrogen sulfates such as the Liu Xue of department of chemistry of Huaibei Coal Normal College is gorgeous are received the synthetic of catalysis diisooctyl fumarate, and take fumaric acid and isooctyl alcohol as raw material, NaHSO4 makees catalyzer, and toluene is made the band aqua, has synthesized diisooctyl fumarate.Guangxi Normal University's chemical is that Liao Ping moral etc. has been studied the Method and process condition that anhydrous cupric sulfate is done catalyzer synthetic diisooctyl fumarate.Synthetic document and the patent reports of other softening agent such as research DEF, non-toxic plasticizer, low molecular weight polyester plasticiser are arranged in addition.It is a kind of new chemical mould inhibitor that 3 phases in 2004 " fine chemistry industry economy and technical intelligence " are introduced DEF (DEF), has low toxicity, efficient, use and be not subjected to pH value limitation, the advantages such as noresidue, be commonly used for organic synthesis intermediate, internal plasticizer and solvent, adopting hydrogen sulfate to receive with aluminum chloride is catalyzer, replaces sulfuric acid and the hydrochloric acid of severe corrosive, take cis-butenedioic anhydride and ethanol as raw material, synthesized DEF.The softening agent cost of these method preparations is higher.

Sour water slag production process: the tail gas that phthalic anhydride production produces forms sour water after washing, the sour water composition is mainly: MALEIC ANHYDRIDE, methyl-maleic acid, phenylformic acid, phthalic anhydride etc., sour water is produced fumaric acid through purifying, make with extra care, reacting, and remaining mixing acid sludge is the sour water slag.Sour water slag Main Components is the mixing acid that the acid such as fumaric acid, MALEIC ANHYDRIDE, methyl-maleic acid, phthalic anhydride, phenylformic acid form.Large-scale phthalic anhydride manufacturing enterprise has hundreds of tons spent acid grain slag to produce every year, processes these waste materials and will spend great amount of cost.How low-cost processes, these waste materials of recycle alleviate the company operation burden becomes the problem that the assistant officer of each manufacturing enterprise need solve.

Reclaim alcohol: the softening agent such as DOP, DINP need underpressure distillation that excessive alcohol is deviate from for reclaiming alcohol in the reaction later stage, and its main component is isooctyl alcohol or isononyl alcohol (more than 80%), remains to be monoesters and other ester class.

Summary of the invention

Technical problem to be solved by this invention is, a kind of can be take above-mentioned waste as raw material production low-grade PVC softening agent is provided, and that reduces softening agent manufacturing cost and fumaric acid production offal treatment cost produces by product and the method that reclaims alcohol and prepare the PVC softening agent with fumaric acid.

Method process following steps of the present invention:

The first step: adding sour water slag and molfraction are 2～4 parts recovery isooctyl alcohol or reclaim isononyl alcohol in the reactor that thermometer, distillation condensing works, whipping appts are housed, the molfraction that the add-on of sour water slag is converted to fumaric acid is 1 part, adds the esterifying catalyst of 200～400ppm again, is heated to 120～160 ℃ of water outlets under stirring state;

Second step: continuing to be warming up to maximum temperature is 220 ℃, and reaction process is controlled all the time and heated up in a steamer 80～102 ℃ of temperature, reacts to acid number to be＜1.0mgKOH/g;

The 3rd step: cooling, be cooled to 195 ℃ when what use in the first step when reclaiming isooctyl alcohol, be cooled to 215 ℃ when what use in the first step when reclaiming isononyl alcohol ,-600～-dealcoholysis of reducing pressure under the 740mmHg condition was stopped reaction in 1～2 hour, cooling is filtered and is got product.

The inventive method successfully utilizes plasticizer production enterprise at the pure Di File softening agent of Chenging with sour water slag He of the recovery of producing DOP, the generation of DINP process, the assessment result that its performance is done shows, the softening agent that the inventive method is synthesized can be used as low-grade cheap softening agent and carries out volume production and use, has effectively utilized scrap materials of enterprises, has reduced production cost and treatment cost of waste liquor, has reduced environmental pollution.

Embodiment

The step of embodiments of the invention is as follows:

The first step: in the reactor that thermometer, distillation condensing works (chuck is arranged), whipping appts are housed, add 1 part of sour water slag, 3.0 parts of recovery isooctyl alcohol, the esterifying catalyst (tin oxalate compounds) that adds again 250ppm, under stirring state, be heated to water outlet (120～160 ℃), second step: continuing to be warming up to maximum temperature is 220 ℃, reaction process is controlled all the time and is heated up in a steamer a temperature at 90～102 ℃, react to acid number less than 1.0mgKOH/g; The 4th step: be cooled to 195 ℃, (680mmHg) stopped reaction after 1 hour, cooling is filtered and is got product, and collects simultaneously the alcohol of deviating from and prepares against recycle in the dealcoholysis of reducing pressure.

It is as follows that the product of the embodiment of the invention detects index:

1. product chemical property:

Project	Acid number mgKOH/g	Moisture %	Viscosity cps	Alcohol content %
					Data	0.40	0.0736	30.6	0.1687

2. plasticizing efficiency and aging resistance:

2.1 plasticizing efficiency

	The softening agent addition	Hardness (Shore A.15sec)
			DOP	60	79
Present embodiment was according to 1: 1 blending DOP	60	80

2.2 machinery and aging resistance

The test piece preparatory condition

Take out the sheet temperature: 165 ℃, take out the sheet time: 5min compressing tablet temperature: 170 ℃, the compressing tablet time: 8min

Aging condition: 100 ℃ of * 168hr

Measuring mechanical property temperature: 25 ℃

Instrument equipment: two running roller machines (the deep sun in Shanghai), tabletting machine (inscription Yu electronics technology company limited), ageing oven (inscription Yu electronics technology company limited), puller system (High Speed Rail Testing Instruments company limited), Shore durometer (Wuxi Qian Zhou surveying instrument factory)

Test piece prescription: PVC powder (S-65) 100g, softening agent 60g, stablizer 3g

Brief summary:

This product and DOP according to blending in 1: 1 after its plasticizing efficiency substantially approaching with DOP, machinery and aging resistance are also more approaching with DOP, but color is dark than DOP, can be used for color depth and reaches in the less demanding PVC goods of color.

Claims (1)

1. produce by product and the method that reclaims alcohol and prepare the PVC softening agent with fumaric acid for one kind, it is characterized in that: the process following steps,

The first step: adding sour water slag and molfraction are 2～4 parts recovery isooctyl alcohol or reclaim isononyl alcohol in the reactor that thermometer, distillation condensing works, whipping appts are housed, the molfraction that the add-on of sour water slag is converted to fumaric acid is 1 part, adds the esterifying catalyst of 200～400ppm again, is heated to 120～160 ℃ of water outlets under stirring state;

Described sour water slag is that the tail gas that phthalic anhydride production produces forms sour water after washing, and sour water is through purification, refining, reaction production fumaric acid, and remaining mixing acid sludge is the sour water slag;

Second step: continuing to be warming up to maximum temperature is 220 ℃, and reaction process is controlled all the time and heated up in a steamer 80～102 ℃ of temperature, react to acid number be＜1.0 mgKOH/g;

The 3rd step: cooling, be cooled to 195 ℃ when what use in the first step when reclaiming isooctyl alcohol, be cooled to 215 ℃ when what use in the first step when reclaiming isononyl alcohol ,-600～-dealcoholysis of reducing pressure under the 740mmHg condition was stopped reaction in 1～2 hour, cooling is filtered and is got product.