CN1032749C - Oil-removing purifying of crude naphthenic acid by amination - Google Patents
Oil-removing purifying of crude naphthenic acid by amination Download PDFInfo
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- CN1032749C CN1032749C CN 93101924 CN93101924A CN1032749C CN 1032749 C CN1032749 C CN 1032749C CN 93101924 CN93101924 CN 93101924 CN 93101924 A CN93101924 A CN 93101924A CN 1032749 C CN1032749 C CN 1032749C
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- naphthenic acid
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- degreasing
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Abstract
The present invention adopts an ammonium extraction technique to remove neutral oil of crude naphthenic acid, and uses a solvent system prepared from methanol, water and ammonia to extract naphthenic acid at the room temperature, and thus, the neutral oil and the naphthenic acid are separated to achieve the purposes of deoiling and refining. The prepared deoiled naphthenic acid has the crude acid value more than 210 mgKOH/g, and has the acid content more than 90*10 <-2>, and the naphthenic acid yield is larger than 90*10 <-2>. The solvent can be recycled.
Description
The present invention relates to a kind of de-oiling technology of naphthenic acid refining technology, particularly crude naphthenic acid.
Contain 15～65 * 10 in the crude naphthenic acid
-2Unsaponifiables (or claim neutral oil), its existence has a strong impact on the application of naphthenic acid.De-oiling is to make crude naphthenic acid reach the important means of industry standard.In the prior art, United States Patent (USP) 4,634,519 (1987) have introduced the method that removes naphthenic acid from the petroleum fractions (180～600 ℃) of acid number greater than 0.2mgKOH/g, this method is the solvent extraction naphthenic acid of forming with liquid alkane alcohol, water and ammonia, but this method only is suitable for the petroleum fractions of dry acid value less than 5mgKOH/g, and the naphthenic acid content that is reclaimed is less than 90 * 10
-2
The crude naphthenic acid de-oiling technology that the objective of the invention is to overcome the deficiencies in the prior art and provide a kind of simple and effective, pollution-free and waste residue to handle problems.
Characteristics of the present invention are the solvent system formed with certain proportion with methyl alcohol, water and ammonia slective extraction naphthenic acid at room temperature, thereby naphthenic acid is separated with neutral oil, reach de-oiling purified purpose.
The present invention is achieved in that and earlier crude naphthenic acid is carried out underpressure distillation, cuts into front-end volatiles (less than 300 ℃), after cut and acid sludge (less than 10 * 10 of total amount
-2) three parts.Will preceding stay the solvent formed of branch and methyl alcohol and ammoniacal liquor, system through settlement separate be two-phase.One is the neutral oil of acid number less than 5mgKOH/g mutually, can be used as the diesel oil blending component after treated (secondary ammoniumization); Then for being rich in the solvent phase of naphthenic acid, except that desolvating, underpressure distillation steams naphthenic acid again, then can obtain acid content greater than 90 * 10 through the normal pressure distillation mutually for another
-2Faint yellow de-oiling naphthenic acid.And the acid content of after cut is greater than 85 * 10
-2, do not need de-oiling and directly obtain the finished product naphthenic acid.
(acid content is 50～85 * 10 to above-mentioned crude naphthenic acid
-2) through the front-end volatiles of underpressure distillation, acid content is 10～70 * 10
-2Between, with 20～50 * 10
-2For good.
In the above-mentioned solvent system, methyl alcohol can be 80～120 ℃ petroleum fractions replacement with ethanol, Virahol or boiling range, preferably uses methyl alcohol.
In the above-mentioned solvent system, the volume ratio of methyl alcohol and ammoniacal liquor is 0.1～9.0: 1, and ammonia content is 1～20 * 10 in the solvent
-2
In the above-mentioned extraction process, the volume ratio of solvent and crude naphthenic acid is 0.25～2.0: 1, and the mol ratio of acid is 0.5～15: 1 in ammonia and the crude naphthenic acid.
In the above-mentioned extraction process, temperature generally 15～50 ℃ ask, is preferably in 20～35 ℃, promptly is suitable for extracting under the room temperature.Solvent is advisable with 0.5～30 minute with the mixing time that contacts of crude naphthenic acid.
Adopt technical scheme of the present invention, de-oiling is effective, and the de-oiling cyclocarboxylic acid content that obtains is 90 * 10
-2More than; Solvent can reclaim usefulness again, and cost is low, without acidifying, reduces and pollutes.
Accompanying drawing is the schema of crude naphthenic acid de-oiling technology.
Below in conjunction with embodiment the present invention is done further statement.
Embodiment 1
In the separating funnel of a 250ml, adding the thick acid number of 50ml is that 85.1mgKOH/g, acid content are 33.6 * 10
-2Crude naphthenic acid, add 30ml methyl alcohol, 7.5ml water and the 12.5ml strong aqua (25～28 * 10 be pre-mixed again
-2), mixture at room temperature fully vibrated 1 minute, at room temperature placed then 5 minutes.Treat after the layering fully two-phase to be separated.The acid number of the neutral oil phase in upper strata is 0.80mgKOH/g.Lower floor's solvent phase is poured in the flask, distills at normal pressure with under 1.33～2.67KPa pressure to obtain solvent and naphthenic acid, and the thick acid number of gained naphthenic acid is 234.1mgKOH/g, and acid content reaches 92.5 * 10
-2, the naphthenic acid yield is 93 * 10
-2
In addition, carried out the intermittent type extraction test by above-mentioned steps again five times with different material, used raw material is during processing condition (room temperature) and experimental result are listed in the table below.
| Naphthenic acid | The solvent composition mass ratio | Ammonia and naphthenic acid | Neutral oil | The de-oiling naphthenic acid | |||
| Sequence number | Thick acid number | Acid content | Ammonia: water: methyl alcohol | Molar ratio | Acid number | Thick acid number | Acid content |
| mgKOH/g | 10 -2 | mgKOH/g | mgKOH/g | 10 -2 | |||
| 1 | 26.1 | 10.1 | 1∶10.1∶13.8 | 1.50 | 0.94 | 233.4 | 90.6 |
| 2 | 73.1 | 28.0 | 1∶2.8∶2.1 | 7.36 | 0.85 | 253.3 | 94.8 |
| 3 | 73.1 | 28.0 | 1∶2.8∶5.1 | 5.02 | 0.61 | 249.3 | 93.0 |
| 4 | 85.1 | 33.6 | 1∶2.8∶5.1 | 4.15 | 1.58 | 238.9 | 94.4 |
| 5 | 85.1 | 33.6 | 1∶8.6∶12.0 | 1.79 | 1.15 | 237.6 | 93.8 |
| 6 | 124.7 | 47.7 | 1∶10.0∶13.6 | 1.50 | 0.33 | 239.4 | 91.6 |
Embodiment 2
By technical process shown in the drawings.Crude naphthenic acid (is regulated the ratio of supplementing solvent and recovery solvent through front-end volatiles and solvent that vacuum still (1) cutting obtains, to keep the ratio between solvent load of the present invention and each component) through volume pump input mixing device (2), mixing device (2) can be a static mixer, mixing column or still etc.The system that mixes enters tripping device (3) immediately, as settlement separate jar, centrifuge separator etc., becomes two-phase after separating.The upper strata is the neutral oil phase of low acid number, enters refining plant (4) (can be ammoniumization or alkaline cleaner) and further removes the blending component that can be used as diesel oil behind the naphthenic acid.The solvent phase that naphthenic acid is rich in lower floor enters distillation tower (5), from the recovered overhead solvent, recycles, and bottoms enters vacuum distillation apparatus (6), obtains acid content greater than 90 * 10 from cat head
-2Light yellow de-oiling naphthenic acid.In addition, also can obtain the purpose product in the direct underpressure distillation of distillation tower (5).
Claims (9)
1. the degreasing refinement process of a crude naphthenic acid is characterized in that being cut into earlier front-end volatiles, after cut and acid sludge, and the volume ratio with methyl alcohol and ammoniacal liquor is 0.1～9.0 then: 1, ammonia content is 1～20 * 10
-2The solvent system that the methyl alcohol of (weight), water and ammonia are formed at room temperature extracts the naphthenic acid of front-end volatiles, and the step that its technology comprises has:
(a) with crude naphthenic acid front-end volatiles and solvent system uniform contact, obtain a kind of immiscible two-phase mixture, one is the solvent phase that is rich in naphthenic acid mutually, another is the neutral oil phase of low acid number mutually;
(b) above-mentioned solvent phase and the neutral oil that is rich in naphthenic acid is separated, solvent phase obtains de-oiling naphthenic acid and solvent through distillation, and neutral oil phase is made the diesel oil blending component after treatment.
2. crude naphthenic acid degreasing refinement process according to claim 1 is characterized in that [acid content is 50～85 * 10 to crude naphthenic acid
-2(weight)] be 10～70 * 10 through the acid content of the front-end volatiles of underpressure distillation
-2(weight).
3. crude naphthenic acid degreasing refinement process according to claim 1 is characterized in that [acid content is 50～85 * 10 to crude naphthenic acid
-2(weight)] be 20～50 * 10 through the acid content of the front-end volatiles of underpressure distillation
-2(weight).
4. crude naphthenic acid degreasing refinement process according to claim 1 is characterized in that the methyl alcohol in the solvent system can be that 80～120 ℃ petroleum fractions replaces with ethanol, Virahol or boiling range.
5. crude naphthenic acid degreasing refinement process according to claim 1 is characterized in that the volume ratio of middle solvent of step (a) and crude naphthenic acid is 0.25～2.0: 1, and the mol ratio of acid is 0.5～15: 1 in ammonia and the raw material naphthenic acid.
6. crude naphthenic acid degreasing refinement process according to claim 1 is characterized in that step (a) is to carry out 15～50 ℃ temperature range, and the contact mixing time was advisable with 0.5～30 minute.
7. crude naphthenic acid degreasing refinement process according to claim 1 is characterized in that step (a) is to carry out 20～35 ℃ temperature range, and the contact mixing time was advisable with 0.5～30 minute.
8. crude naphthenic acid degreasing refinement process according to claim 1, it is characterized in that in the step (b) that separated solvent phase adopts first air distillation to remove and desolvates, the method that the back decompression steams naphthenic acid makes solvent separate with naphthenic acid, obtain the de-oiling naphthenic acid, and can reclaim 90 * 10
-2Above solvent, solvent can recycle.
9. crude naphthenic acid degreasing refinement process according to claim 1 is characterized in that this technology is to carry out at intermittence or successive mode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93101924 CN1032749C (en) | 1993-02-26 | 1993-02-26 | Oil-removing purifying of crude naphthenic acid by amination |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93101924 CN1032749C (en) | 1993-02-26 | 1993-02-26 | Oil-removing purifying of crude naphthenic acid by amination |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1091416A CN1091416A (en) | 1994-08-31 |
| CN1032749C true CN1032749C (en) | 1996-09-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93101924 Expired - Fee Related CN1032749C (en) | 1993-02-26 | 1993-02-26 | Oil-removing purifying of crude naphthenic acid by amination |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072641C (en) * | 1998-08-14 | 2001-10-10 | 中国石油化工集团公司 | Process for separating and recovering naphthenic acid from fractional oil of petroleum |
| CN100506949C (en) * | 2006-04-18 | 2009-07-01 | 中国海洋石油总公司 | Method of eliminating naphthenic acid from crude oil or fraction oil |
| CN114214121B (en) * | 2021-12-14 | 2024-02-20 | 浙江东江能源科技有限公司 | Preparation device and preparation method of high-quality low-sulfur biodiesel |
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- 1993-02-26 CN CN 93101924 patent/CN1032749C/en not_active Expired - Fee Related
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