CN1126749A - Method of removing basic nitrogen compound from oils - Google Patents
Method of removing basic nitrogen compound from oils Download PDFInfo
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- CN1126749A CN1126749A CN 95101062 CN95101062A CN1126749A CN 1126749 A CN1126749 A CN 1126749A CN 95101062 CN95101062 CN 95101062 CN 95101062 A CN95101062 A CN 95101062A CN 1126749 A CN1126749 A CN 1126749A
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Abstract
The present invention belongs to refining techn in petroleum processing, and it features that acid water solution is mixed with and contacted to oil so as to make the basic nitride in oil dissolve for removal. The said method has high removal rate of basic nitride.
Description
The present invention relates to the purification techniques of petroleum refining process.
In oil, exist impurity compounds such as micro-sulphur compound, nitrogen compound, oxygen compound.In the elementary course of processing of oil, these impurity compounds are transferred to corresponding intermediates---go in the oil product.And from oil product, remove a main process---the treating process that these impurity compounds are refining of petroleum.In these impurity compounds, basic nitrogen compound has the greatest impact to the stability of oil product, and it can cause oil oxidation, generates colloid, makes the debase of oil product.Existing oil purification method mainly contains two kinds: a kind of is the hydrofining method; Another kind is the sulfuric acid treatment method.Hydrofinishing process and method of the present invention differ bigger, so not foreign stating.The sulfuric acid treatment method is the technology that the fifties, petroleum refining industry adopted.According to 8 pages of the 1st phases of " refining of petroleum " nineteen fifty-seven and the 12 pages of introductions of 1958 1 phases, its process is under certain temperature condition, is that the vitriol oil and oil product more than 90% mixes according to a certain percentage and enter settlement separate jar then with concentration.Impurity compound generation chemical reaction in sulfuric acid and the oil product.The product of chemical reaction is macromolecular condenses, is commonly referred to acid sludge.The proportion of acid sludge makes acid sludge be sunken to the slurry tank bottom greater than the proportion of oil product through sedimentation.Emit then and make it to separate with oil product.The sulfuric acid treatment fado is periodical operation.Sulfuric acid once mixes by mixing tank with oil product.Can not circulate.Sulfuric acid treatment method oil product refining losses is big.And the acid sludge that produces in the treating process is waste, contaminate environment.In petroleum refining process, the sulfuric acid treatment method is replaced by the hydrofining method now.Up to the present, other method of sulfuric acid treatment or patent have not been seen as yet.
The invention provides a kind of and hydrofining method different and close oil purification method fully with the sulfuric acid treatment method.The principle of the inventive method is to utilize basic nitrogen compound can be dissolved in the characteristics of acidic aqueous solution, with the sour acidic aqueous solution that is made into suitable concentration, basic nitrogen compound is dissolved in wherein, and in this process, does not produce the reaction of acid sludge.The purpose of present method is to remove the basic nitrogen compound that oil stability is had the greatest impact specially.
Method of the present invention can realize like this; Hydrochloric acid, acetic acid or sulfuric acid and water are mixed with acidic aqueous solution according to a certain percentage in the complex acid jar.Take out acidic aqueous solution and the oil product in the oil tank in the complex acid jar respectively and under certain temperature and ratio, enter mixing tank together with acidic aqueous solution pump and oil pump again, mix contact.Basic nitrogen compound in the oil product is dissolved in the acidic aqueous solution.Mixed solution enters settlement separate jar then.Because of oil product proportion is little, lead to the product after refining settlement separate jar from separating tank top.Acidic aqueous solution is sunken to the bottom of separating tank.When acidic aqueous solution recycles; Sending mixing tank back to by acidic aqueous solution pump extraction acidic aqueous solution recycles.Acidic aqueous solution will be according to the basic n content index periodic replacement of refining back oil product.When acidic aqueous solution does not recycle; Can directly enter neutralization tank by slurry tank bottom relief outlet.Method of the present invention also can realize like this: with carbonic acid gas, water, oil product according to a certain percentage, send into mixing tank together and mix contact under certain temperature, pressure.Carbonic acid gas and water formation acidic aqueous solution and basic nitrogen compound are dissolved in acidic aqueous solution to carry out simultaneously.Perhaps at first carbonic acid gas is become acidic aqueous solution with hydration, and then the synthetic acidic aqueous solution is mixed according to a certain percentage with oil product contact, then mixed solution enter settlement separate jar settlement separate.Surplus carbon dioxide with refining after oil product discharge by the top of separating tank.Acidic aqueous solution falls to the bottom of separating tank and discharges system.
In the method for the invention, the concentration of acid is the key factor that influences denitrification percent in the acidic aqueous solution, in oil product kind, temperature, ratio of mixture one regularly, increases the concentration of acid, and then basic nitrogen compound is dissolved in the solubleness increase of acidic aqueous solution, and denitrification percent increases.But after the concentration of acid increases to a certain degree, increase the concentration of acid again, the anticorrosion grade of equipment and voltage withstand class are increased, and the velocity of variation of denitrification percent diminishes.So, in the method for the invention, the suitable concentration of various acid in acidic aqueous solution is: sulfuric acid is 3～10% (weights), hydrogen chloride content is that the hydrochloric acid of 31% (weight) is 4～10% (weights), acetic acid is 10～40% (weights), and the synthesis pressure of carbonic acid gas acidic aqueous solution or blend pressure are 0.8～2.0MPa (cutting off).But various acid use range in the method for the invention can be: hydrochloric acid (hydrogen chloride content is 31% (weight)), and 0～100% (weight), acetic acid 0～100%, the synthetic or blend pressure of carbonic acid gas is greater than 0.1MPa (cutting off).Because of the increase with its concentration in acidic aqueous solution, the basic nitrogen decreasing ratio improves to sulfuric acid, and the material that sulfonation reaction easily takes place in the oil product simultaneously with acid sulfonation reaction takes place, and the degree that produces acid sludge also increases thereupon.And the generation sulfonation reaction, outside the Pass having, also with relevant, promptly relevant with the kind of oil product by the content of easy sulfonation material in the refined oil with the concentration of sulfuric acid in acidic aqueous solution.Therefore, the refining different the highest working concentration of oil product vitriolic is different, and sulfonation reaction does not promptly take place, and the maximum concentration that produces acid sludge is different.Estimate refining different oil product, the maximum concentration of sulfuric acid in acidic aqueous solution reaches sulfonation reaction do not take place, the defining standard that does not produce acid sludge is: mix under the condition that contacts at oil product and acidic aqueous solution, and at oil product and acidic aqueous solution at settlement separate jar in the settlement separate time, the water-soluble liquid phase two-phase interface of the oil phase on upper strata and lower floor is clear, and two-phase is respectively the oil phase that dissolves each other fully and the acidic aqueous solution that dissolves each other fully mutually.Not having coalescent particle at oil phase occurs.Not having water-insoluble mutually at acidic aqueous solution occurs.Therefore, to refining different oil product, the maximum concentration of available this Standard Selection sulfuric acid in acidic aqueous solution.To the virgin kerosene fraction of certain crude production, the maximum permissible concentration of sulfuric acid in acidic aqueous solution can reach 65% (weight).And in actual treating process,, can guarantee that treating process does not produce acid sludge as long as be lower than maximum concentration.In the method for the invention, solved ortho-sulfuric acid method for refining generation acid sludge by changing sour kind and reducing sour concentration, oil product loses the problem of big and the settlement separate difficulty of acid sludge.This also is the essential distinction of method of the present invention and ortho-sulfuric acid method for refining.
It is 120 to remove basic nitrogen compound to molecular-weight average is 350 oil product that method of the present invention is applicable to from molecular-weight average.Along with the solubleness decline of increase oil product neutral and alkali nitrogen compound in acidic aqueous solution of molecular weight, denitrification percent diminishes.Therefore to change the mixing contact conditions and improve denitrification percent.
In sum, the difference of visible method of the present invention and ortho-sulfuric acid method for refining is: method 1. of the present invention is except that can using hydrochloric acid, acetic acid and carbonic acid gas with the sulfuric acid.2. method of the present invention is mixed contact process chemical reaction is not taken place, generation be dissolution process, be chemical reaction and the sulfuric acid treatment method mixes that contact takes place.3. method of the present invention, acidic aqueous solution can recycle, and the full back of closing regularly replaces.Promptly discharge system after also can using once.4. method of the present invention only removes the basic nitrogen compound that oil stability is had the greatest impact.Therefore, method of the present invention is compared with the ortho-sulfuric acid method for refining and had the following advantages: 1. present method does not produce acid sludge, and the oil product loss is little, and is suitable with the hydrofining method.Solved the ortho-sulfuric acid method for refining and produced acid sludge, the oil product refining losses is big, problem of environment pollution caused.2. method technology of the present invention is simple, and equipment is few, does not exist acid sludge to remove storing specific equipment and operation.3. method basic nitrogen compound decreasing ratio of the present invention reaches as high as more than 88%.Oil stability is good, is that 221 secondary processing diesel oil can be stored nondiscoloration more than 6 months after refining to molecular weight.4. method processing charges of the present invention is low, is 1/5～1/10 of existing hydrogenation method.5. method acidic aqueous solution of the present invention can recycle, thereby the acid consumption is little.
The following stated embodiment describes the present invention in detail, and in these embodiments, unless otherwise indicated, all umbers and per-cent are all by weight.Nitrogen content is a basic n content, and unit is PPM.
Embodiment 1
In the present embodiment, acidic aqueous solution is formulated by 98% sulfuric acid and water.The concentration of preparation back alkali acid is 1.5%.The oil product molecular-weight average of processing is 221, and nitrogen content is 205.The ratio of mixture of acidic aqueous solution and oil product is 4: 1.Mixing the contact temperature is 40 ℃.By this condition, oil product enters mixing tank with acidic aqueous solution and mixes contact.Enter separating tank then.Separating tank stop 45 minutes settlement separate, oil product flows out from top.Acidic aqueous solution is sunken to settlement separate pot bottom and sends mixing tank and the use of oil product mixed cycle back to by the extraction of sour water pump.It is 62 that oil product takes off the back nitrogen content, and denitrification percent is 70%.The acidic aqueous solution that the regular discharging of acidic aqueous solution more renews is qualified to guarantee purified oil alkalinity nitrogen index.
Embodiment 2
In the present embodiment, acidic aqueous solution also is to be prepared by sulfuric acid.The concentration of sulfuric acid in acidic aqueous solution is 65%, and the oil product molecular-weight average of processing is 160, and nitrogen content is 9, and the ratio of mixture of acidic aqueous solution and oil product is 1: 20.Mixing the contact temperature is 40 ℃.By this condition, mix contact, separate with method similarly to Example 1, it is 0 that oil product takes off the back nitrogen content.Denitrification percent is 100%.The acidic aqueous solution of settlement separate pot bottom is directly discharged system, does not recycle.
Embodiment 3
In the present embodiment, acidic aqueous solution is the preparation of 31% hydrochloric acid by hydrogen chloride content, and the concentration of preparation back hydrochloric acid is 0.7%.The oil product molecular-weight average of processing is 221, and nitrogen content is 205, and the ratio of mixture of acidic aqueous solution and oil product is 4: 1, and mixing the contact temperature is 40 ℃.By this condition, mix contact, separate with method similarly to Example 1.It is 68 that oil product takes off the back nitrogen content, and denitrification percent is 66%.Acidic aqueous solution at the bottom of the slurry tank recycles, regular update.
Embodiment 4
In the present embodiment, acidic aqueous solution is prepared by hydrochloric acid, and the concentration of preparation back acid is 70%.The oil product molecular-weight average of processing is 118, and nitrogen content is 6, and acidic aqueous solution is 1: 20 with the ratio of oil product.Mixing the contact temperature is 40 ℃.By this condition, acidic aqueous solution contacts, separates with the oil product mixed once.After the separation, acidic aqueous solution had both been discharged system, and it is 0 that oil product takes off the back nitrogen content, and denitrification percent is 100%.
Embodiment 5
In the present embodiment, acidic aqueous solution is prepared by acetic acid, and the concentration of preparation back acid is 6%.The oil product molecular-weight average of processing is 148, and nitrogen content is 89.Acidic aqueous solution is 8: 1 with the ratio of oil product.Mixing the contact temperature is 40 ℃, by this condition, mixes contact, separates with method similarly to Example 1.It is 33 that oil product takes off the back nitrogen content, and denitrification percent is 74%.Acidic aqueous solution recycles, periodic replacement.
Embodiment 6
In the present embodiment, acidic aqueous solution is prepared by acetic acid, and the concentration of preparation back acid is 40%, and the oil product molecular-weight average of processing is 221, and nitrogen content is 205.Acidic aqueous solution and the ratio of oil product are to mix that to contact temperature be 40 ℃ at 4: 1.By this condition, mix contact, separate with method similarly to Example 1.It is 24.6 that oil product takes off the back nitrogen content, and denitrification percent is 88%.Acidic aqueous solution recycles periodic replacement.
Embodiment 7
In the present embodiment, the molecular-weight average of oil product is 221, and nitrogen content is 205.Acid is carbon dioxide.Carbonic acid gas, water and oil product pass through mixing tank in 2.5: 200: 100 ratio jointly under the pressure of 40 ℃ temperature, 0.8MPa.Enter then with depressing separating tank.Unabsorbed carbon dioxide gas and oil product flow out from the top of separating tank, and acidic aqueous solution is discharged system in the bottom of separating tank.Taking off back oil product nitrogen content is 98, denitrification percent 52%.
Embodiment 8
In the present embodiment, the molecular-weight average of oil product is 221, and nitrogen content is 205, and acidic aqueous solution is to be 1.8MPa at pressure, and temperature is under 30 ℃ of conditions, by carbonic acid gas and water synthetic.Synthetic back acidic aqueous solution contacts with the mixed of oil product with 2: 1, and mixing temperature is 40 ℃.Mixed mixed solution enters with the settlement separate jar of depressing settlement separate, and a spot of carbon dioxide and oil product are discharged from the top of separating tank.Acidic aqueous solution is discharged system from the bottom of separating tank.The nitrogen content of taking off the back oil product is 88, and denitrification percent is 57%.
Claims (7)
1, a kind of method that from oil product, removes basic nitrogen compound.It is characterized in that hydrochloric acid, acetic acid or sulfuric acid and water are mixed with acidic aqueous solution by a certain percentage in the complex acid jar.At this moment take out respectively with sour water pump and oil pump again that oil product enters mixing tank together and mixes contact in acidic aqueous solution in the complex acid jar and the oil product jar under certain temperature and ratio.It is settlement separate that mixed mixed solution enters settlement separate jar.Oil product leads to the product after making with extra care from settlement separate jar of top.Acidic aqueous solution sinks to settlement separate jar bottom.When acidic aqueous solution recycles, send into mixing tank and the use of oil product mixed cycle again by the extraction of sour water pump.The full back of closing of acidic aqueous solution regularly replaces.When not recycling, extract direct discharge system out by the sour water pump.
2, a kind of method that from oil product, removes basic nitrogen compound.It is characterized in that carbonic acid gas, water and oil product under certain temperature, pressure condition, enter mixing tank according to a certain percentage jointly and mix contact that perhaps carbonic acid gas and the water elder generation synthetic acidic aqueous solution mixes contacting again with oil product.It is settlement separate that mixed solution enters settlement separate jar then.Surplus carbon dioxide gas and oil product are discharged from the top of jar.The acidic aqueous solution at the jar end is by slurry tank bottom discharge system.
3, by claim 1 and the 2 described methods that remove basic nitrogen compound from oil product, the acidic aqueous solution that it is characterized in that dissolving oil product neutral and alkali nitride can use hydrochloric acid, acetic acid, sulfuric acid or carbonic acid gas and water formulated according to a certain percentage.
4, by claim 1 and 3, by the acidic aqueous solution of hydrochloric acid preparation.The safe level of hydrochloric acid is less than 100 (weight) %.
5, by claim 1 and 3, by the acidic aqueous solution of sulfuric acid preparation, the sulfuric acid maximum concentration is less than 65 (weight) %.
6, want 1 and 3 acidic aqueous solutions by the acetic acid preparation by right, the safe level of acetic acid is less than 100 (weight) %.
7,, it is characterized in that and from molecular-weight average is 120 to 350 oil product, to remove basic nitrogen compound by the described method that from oil product, removes basic nitrogen compound of claim 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95101062 CN1126749A (en) | 1995-01-14 | 1995-01-14 | Method of removing basic nitrogen compound from oils |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95101062 CN1126749A (en) | 1995-01-14 | 1995-01-14 | Method of removing basic nitrogen compound from oils |
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| CN1126749A true CN1126749A (en) | 1996-07-17 |
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| CN 95101062 Pending CN1126749A (en) | 1995-01-14 | 1995-01-14 | Method of removing basic nitrogen compound from oils |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102876362A (en) * | 2012-10-22 | 2013-01-16 | 常州大学 | Diesel refinement and decolorization method |
| CN110627623A (en) * | 2019-09-06 | 2019-12-31 | 陕西煤业化工集团神木天元化工有限公司 | Separation system and method for alkaline nitride in phenol product |
-
1995
- 1995-01-14 CN CN 95101062 patent/CN1126749A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102876362A (en) * | 2012-10-22 | 2013-01-16 | 常州大学 | Diesel refinement and decolorization method |
| CN110627623A (en) * | 2019-09-06 | 2019-12-31 | 陕西煤业化工集团神木天元化工有限公司 | Separation system and method for alkaline nitride in phenol product |
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