CN1071445A - Replace sulfuric acid to improve waste oil regeneration acid-earth process with many ethylenes amine flocculation agent - Google Patents

Abstract

A kind of many ethylenes of usefulness amine flocculation agent replaces sulfuric acid to improve waste oil regeneration acid-earth process, and said many ethylenes amine flocculation agent makes by ethylene dichloride and ammoniacal liquor hot pressure reaction, contains the ethylene group (CH more than 2 or 2 in their molecule ₂-CH ₂-) and amino (NH ₂).It is characterized in that, make the proportion of flocculation agent higher by 0.08～0.1 than waste oil, flocculation agent add-on (volume) is 1～3% of a waste oil volume, under 40～90 ℃ of conditions of temperature, in pending waste oil, add flocculation agent while stirring, when the volume of handling waste oil is 1 liter, only need to stir 2～5min, again leave standstill 0.5～1h after, waste oil impurity promptly has tangible cohesion and sedimentation phenomenon, this type of flocculation agent can add at the waste oil pretreatment stage, also can after distillation, add, but add better effects if to distill the back.

Description

Replace sulfuric acid to improve waste oil regeneration acid-earth process with many ethylenes amine flocculation agent

The present invention relates to a kind of many ethylenes of usefulness amine flocculation agent and replace sulfuric acid to improve waste oil regeneration acid-earth process, belong to the treatment process of waste oil regeneration.

Waste oil refers to the lubricating oil of scrapping through use here, as used oil, comprises gasoline engine oil and diesel engine oil.These waste oil adopt acid-earth process to carry out manipulation of regeneration usually.Promptly earlier waste oil is carried out pre-treatment with the settled method of heating, remove free water content and impurity, remove light ends through distillation again, comprise the water and gasoline or the diesel oil that do not eliminate, mix with the vitriol oil then, make the carbon granule, impurity and the lubricating oil additive that are suspended in the oil form acid sludge and separate out from oil, the oil of removal acid sludge neutralizes with alkali and carclazyte and adsorbs, filters, obtain lubricant base, adding specific lubricating oil additive at last becomes recycled product oil.

Yet, modern mechanical particularly oil engine improves day by day to the performance and the specification of quality of lubricating oil, contained additive such as oxidation inhibitor, detergent-dispersant additive, viscosity index improver etc. in the oil, content increases gradually, make regenerative process become difficult more, not only need to increase the vitriolic consumption, prolong the time that acid sludge is separated out, and reduced oily yield and quality.The unsurmountable disadvantage of acid-earth process also is distillation and when adding acid treatment, produces a large amount of stinks and sour gas, and useful component is not only destroyed in the waste oil, and produce a large amount of acid sludges (for the waste oil amount 15～20%), handle very difficult.It has concentrated the major impurity in the waste oil; contain objectionable impuritiess such as metals such as more free sulfuric acid and lead, iron, copper, cadmium, zinc, barium, calcium and polycyclic aromatic hydrocarbons; the employing way of burning or burying no matter all can be caused environmental pollution and is subjected to the restriction of environment protection.Therefore, existing acid-earth process is faced with by new technology and replaces.

Waste oil after the distillation contains a large amount of solia particles, and its particle diameter and contains colloid all below 5um, is difficult to filter, and can not separate in slurry tank or whizzer.As avoid using sulfuric acid, and then need in oil, to add specific flocculation agent, just can make the soot particles, colloid and the various metallics that are dispersed in the oil form condensation product and from oil, separate by cohesion.According to patent retrieval and reported in literature, the flocculation agent that is used for the waste oil purification has both at home and abroad reached hundreds of.Wherein maximum with organic compound or polymkeric substance kind, comprise water soluble and have surface-active organic oxygen-containing compound or nitrogenous compound, as Organometallic complex agent such as organic couplers such as corresponding alcohols, acids, ester class, ketone, ethers or amine and anthranilic acid and polymeric amide etc.But all these flocculation agent all are to utilize organic solvent such as toluene, dimethylbenzene, alcohols or ester class etc. to make its dissolving or make dispersion agent or coagulant aids with other material, wiring solution-forming uses, and this type of solvent volatility is big, and poisonous, inflammable, poor stability has brought difficulty to subsequent handling.

In order to solve the problem that flocculation agent exists in the waste oil purification applications, the inventor has done research to the various materials of impurity cohesion in the used oil that can make.The result of research is that the impurity in the oil will soon condense if many ethylenes amine flocculation agent directly is added in the waste oil, and through centrifugation, impurity can separate rapidly totally.Like this, replace sulfuric acid, just can reach the purpose of improving existing acid-native technology of waste oil regenerating according to the acid sludge source of pollution that acid-earth process brought with many ethylenes amine flocculation agent.

Above-mentioned many ethylenes amine flocculation agent is by ethylene dichloride and ammoniacal liquor hot pressure reaction and get.In their molecule, contain the ethylene group (CH more than 2 or 2 ₂CH ₂-) and amino (NH ₂), its representative structure can be expressed as:

(1) Diethylenetriaminee (DETA) DETA(Diethylenetriamine)

H ₂N-CH ₂CH ₂-NH-CH ₂CH-NH ₂

(2) triethylenetetramine TETA(Triethylenetramine)

H ₂N-（CH ₂CH ₂-NH） ₂-CH ₂CH ₂-NH ₂

(3) tetraethylenepentamine TEPA(Tetraethylenetramine)

H ₂N-（CH ₂CH ₂-NH） ₂-CH ₂CH ₂-NH ₂

(4) multiethylene polyamine PEPA(Polyethylenepolyamine)

H ₂N-(CH ₂CH ₂-NH) _N＞4-CH ₂CH ₂-NH ₂, and their isomer, as:

(5) aminoethyl piperazine AEP(Aminoothylene-piperazine)

The physical properties such as the table 1 of above-mentioned many ethylenes amine representative.Many ethylenes amine specification of quality such as table 2 as the flocculation agent use.

The listed ethylene amine more than four kinds of table 2 flocculation agent, its molecular weight (103.17～232.38) has dispersiveness.The proportion of its mixture has additive properties, can get its mean value by mixing rule, it is 0.967 that DETA gets (0.954+0.980)/2, it is 0.985 that TETA gets (0.975+0.995)/2, TEPA gets (0.990+1.010)/2 promptly 1, and PEPA gets (1.000+1.040)/2 and promptly 1.02 calculates by additive properties.

$\mathrm{d\; m\; =}\underset{\mathrm{i\; =\; 1}}{\overset{\mathrm{n\; =\; 4}}{\mathrm{\Σ}}}\mathrm{d\; i\; ·\; v\; i}$

In the formula: dm-flocculation agent mixture proportion;

The proportion of various many ethyleneamineses flocculation agent (mean value) in the di-mixture;

The percentage by volume of various many ethyleneamineses flocculation agent in the vi-mixture.

Do not need during use again through purifying, but according to the proportion of institute's waste oil to be processed, the proportion of adjustment flocculation agent.Generally speaking, make the proportion of flocculation agent higher by 0.08～0.1 than waste oil, flocculation agent add-on (volume) is 1～3% of a waste oil volume, under 40～90 ℃ of conditions of temperature, in pending waste oil, add flocculation agent while stirring, when processing waste oil volume is 1 liter, only need to stir 2～5 minutes, again leave standstill 0.5～1h after, impurity promptly has tangible cohesion and sedimentation phenomenon in the waste oil, this type of flocculation agent can add at the waste oil pretreatment stage, also can after distillation, add, but add better effects if to distill the back.

Because many ethylenes amine flocculation agent molecular weight has dispersiveness, many ethyleneamineses that molecular weight is low can make high being dissolved in the oil better of molecular weight.Because various many ethyleneamineses molecular structures all contain ammonia (NH ₂Or-NH-), the lone electron pair of nitrogen in the amino (N) atom has reduced cloud density because of the attraction that is subjected to oxygen (O) atom in the oily inner oxide impurity, make hydrogen (H) atom that is connected with nitrogen (N) atom lively, and then generate hydrogen bond with oxygen (O) atom.Like this, many ethyleneamineses molecule can pass through hydrogen bond and bonding with various oxide impurities in the oil, produces coherent structure.The longer multiethylene polyamine of molecular chain can wind up condensation product, and contaminant particles is comprised lose carbon granule of oxide compound liquid film protection to be assembled and become big, thus can sedimentation in oil, impurity is separated with oil.

As mentioned above, replace sulfuric acid with many ethylenes amine flocculation agent, existing acid-earth process is improved, its effect is:

(1) fundamentally solves acid-earth process because of producing the problem of environmental pollution that acid sludge causes, reduced pollutant discharge of enterprise expense and environmental pressure;

(2) yield of self-cleaning oil is improved more than 15～20%, waste oil viscosity is big more, pollution level is dark more, and flocculating result is obvious more, and the yield of oil improves big more;

Confirm through Infrared spectroscopy that (3) suspended impurity remains with still unspent additive through the flocculation agent precipitation and after separating in the waste oil in the oil phase, and these additives destroy all during with vitriolization;

(4) the souring slag is the byproduct that economic worth is arranged.From oil, separate the black ointment that obtains, can be used as the raw material of printing ink and emulsified bitumen, use for printing, building industry;

(5) operate simple and easy, safety, can continue to use some equipment of acid-earth process.Self-cleaning oil after coagulative precipitation and separation can replenish the additive of loss through the carclazyte adsorption filtration, promptly can be made into processed oil.

Example one

The oily I of raw materials used oil is for removing useless No. 20 marine diesel engine oils of light ends.The physical and chemical index such as the table 3 of oil I and agglomeration separation gained self-cleaning oil.Many ethylenes amine flocculation agent and agglomeration separation technical qualification such as the table 4 used at this grease separation.

[notes]: consist of: DETA3%, TETA4%, TEPA56%, PEPA37% according to the flocculation agent that oily I is screened.The proportion dm of this mixture can calculate by aforementioned calculation method, that is: dm=0.967 * 3%+0.985 * 4%+1 * 56%+1.02 * 37%=1.0058.In the example afterwards, promptly using the proportion of flocculation agent mixture, also is to get according to the flocculation agent of formation testing screening is formed to calculate.

Example two

Raw materials used oil oily II-1, II-2.Oil II-1 is useless QE level SAE, 15W/30 gasoline engine oil, and oily II-2 is for useless CC level SAE, 15W/40 diesel engine oil, all without distillation.The physical and chemical index such as the table 5 of oil II-1, II-2 and corresponding self-cleaning oil 1, self-cleaning oil 2.Many ethylenes amine flocculation agent and agglomeration separation technical qualification such as the table 6 selected for use at oily II-1, II-2.

After oil I, oily II-1 and the separating obtained ointment balanced mix of II-2, measuring its oleaginousness behind 160 ℃ of temperature, time 6h is 28.99%, after removing oil, its constituent content is: C82.75% H12.01%, N3.31%, S 1.0%, Zn 0.05%, Fe0.12%, Al0.02%, Cu 0.01%, Ni 4.2ppm.Can be used as ink raw materials or asphalt emulsifier use through experiment.

Claims (2)

1, a kind of many ethylenes of usefulness amine flocculation agent replaces sulfuric acid to improve waste oil regeneration acid-earth process, and said many ethylenes amine flocculation agent makes by ethylene dichloride and ammoniacal liquor hot pressure reaction, contains the ethylene group (CH more than 2 or 2 in their molecule ₂-CH ₃-) and amino-(NH ₂), it is characterized in that, make the proportion of flocculation agent higher by 0.08～0.1 than waste oil, flocculation agent add-on (volume) is 1～3% of a waste oil volume, under 40～90 ℃ of conditions of temperature, in pending waste oil, add flocculation agent while stirring, when handling waste oil is that volume is when being 1 liter, only need to stir 2～5min, again leave standstill 0.5～1h after, waste oil impurity promptly has tangible cohesion and sedimentation phenomenon, this type of flocculation agent can add the treatment stage that waste oil gives, and also can add after distillation, but add better effects if to distill the back.

2, technology according to claim 1 is characterized in that said many ethylenes amine flocculation agent comprises:

(1) Diethylenetriaminee (DETA) DETA(Diethylenetriamine)

H ₂N-CH ₂CH ₂-NH-CH ₂CH-NH ₂

(2) triethylenetetramine TETA(Triethylenetramine)

H ₂N-（CH ₂CH ₂-NH） ₂-CH ₂CH ₂-NH ₂

(3) tetraethylenepentamine TEPA(Tetraethylenetramine)

H ₂N-（CH ₂CH ₂-NH） ₃-CH ₂CH ₂-NH ₂

(4) multiethylene polyamine PEPA(Polyethylenepolyamine)

H ₂N-(CH ₂CH ₂-NH) _N＞4-CH ₂CH ₂-NH ₂, and their isomer

(5) aminoethyl piperazine AEP(Aminoethylene-piperazine)