阅读说明：本技术 一种组合式连续生产酸化油的方法 (Combined continuous production method of acidified oil ) 是由 郭凯 于 2021-10-11 设计创作，主要内容包括：本发明涉及一种组合式连续生产酸化油的方法,将一定比例的皂脚或油脚和水混合,用泵加压并加热后,与酸性气体混合,送至第一反应部分,所得第一反应产物送至第一分离部分,分离出水、油和气体,油相送至第二反应部分,补充水和酸性气体,所得第二反应产物送至第二分离部分,分离出无磷酸化油、含磷脂皂脚或油脚、水和气体,含磷脂皂脚或油脚送至第三反应部分,并加入强酸和水,所得第三反应产物送至第三分离部分分离,含盐废水外排,粗酸化油送至第四分离部分再次静置分离,得到含酸水相、含磷脂酸化油和植物沥青；可以减少含强酸废液的排放,大大降低了污水处理的负担,并且可以得到不含磷脂的优质酸化油,为酸化油的后续加工提供方便。(The invention relates to a combined method for continuously producing acidified oil, which comprises the steps of mixing soapstock or oil foot with water in a certain proportion, pressurizing and heating the mixture by a pump, mixing the mixture with acid gas, sending the mixture to a first reaction part, sending an obtained first reaction product to a first separation part, separating water, oil and gas, sending an oil phase to a second reaction part, supplementing water and acid gas, sending an obtained second reaction product to a second separation part, separating phosphorus-free acidified oil, phosphorus-containing soapstock or oil foot, water and gas, sending the phosphorus-containing soapstock or oil foot to a third reaction part, adding strong acid and water, sending an obtained third reaction product to a third separation part for separation, discharging salt-containing wastewater, sending crude acidified oil to a fourth separation part for standing separation again to obtain an acid-containing water phase, phosphorus-containing acidic oil and plant asphalt; can reduce the discharge of strong acid-containing waste liquid, greatly reduce the burden of sewage treatment, and can obtain high-quality acidified oil without phospholipid, thereby providing convenience for the subsequent processing of the acidified oil.)

1. A combined method for continuously producing acidified oil is characterized in that: the method comprises the following steps:

(1) in the raw material mixing part, the soapstock or the oil foot is fully mixed with a certain proportion of water, and is pressurized by a pump and heated to 60-120 ℃, and then is mixed with acid gas and sent to the first reaction part;

(2) in the first reaction part, the acid gas is dissolved in water to form acid liquor, the acid liquor stays for 2 to 8 hours under the conditions that the pressure is 0 to 15Mpa and the temperature is 60 to 120 ℃, and the weight ratio of water to soapstock or oil stock is 0.5 to 3.0: 1, continuously reacting soapstock or oil residue with the acid liquor to obtain a first reaction product;

(3) in the first separation part, the first reaction product completes three-phase separation of oil, water and gas to obtain first separated gas, a first water phase and a first oil phase, the first separated gas is discharged to a torch system for incineration, the first water phase is discharged to a sewage treatment system for treatment, and the first oil phase is sent to the second reaction part;

(4) in the second reaction part, supplementing water and acid gas into the first oil phase, and staying for 1-5h under the conditions of 0-15MPa of pressure and 60-120 ℃ of temperature, wherein the weight ratio of water to soapstock or oil stock is 0.5-3:1, continuously reacting the first oil phase with acid liquor to obtain a second reaction product;

(5) in the second separation part, the second reaction product is separated into a second separation gas, a second oil phase, a phospholipid-containing soapstock or oil foot and a second water phase, the second separation gas returns to the first reaction part for recycling, the second oil phase is sent out as a non-phosphorylated oil product, the second water phase returns to the first reaction part for water supplement of the first reaction part, and the phospholipid-containing soapstock or oil foot is sent to a third reaction part;

(6) in the third reaction part, after the phosphate-containing soapstock or oil foot is mixed with a certain proportion of 30-40% strong acid aqueous solution by mass, the mixture continuously reacts under the conditions that the pressure is 0-10MPa and the temperature is 50-100 ℃, and the obtained third reaction product is sent to the third separation part;

(7) in the third separation part, the third reaction product is separated into a third water phase containing strong acid salt crystals and a third oil phase containing partial acid liquor, the third water phase containing the strong acid salt crystals is discharged to a sewage treatment system, and the third oil phase containing partial acid liquor is sent to a fourth separation part;

(8) and in the fourth separation part, the third oil phase containing partial acid liquid is separated into phospholipid-containing acidified oil, vegetable asphalt and an acid-containing water phase, the acid-containing water phase returns to the third reaction part for recycling, and at least one part of the phospholipid-containing acidified oil returns to the third reaction part to be mixed with the phospholipid-containing soapstock or oil stock.

2. The combined continuous production method of acidified oil according to claim 1, characterized in that: in the step (2), the reaction conditions of the first reaction part are as follows: the temperature is 80-110 ℃, the pressure is 2.0-8.0MPa, the retention time is 3-5h, and the ratio of water to soapstock or oil residue is 1-2.5: 1.

3. the combined continuous production method of acidified oil according to claim 1, characterized in that: in the step (4), the reaction conditions of the second reaction part are as follows: the temperature is 80-110 ℃, the pressure is 2.0-8.0MPa, the retention time is 2-3 hours, and the ratio of water to soapstock or oil residue is 1-2.5: 1.

4. the combined continuous production method of acidified oil according to claim 1, characterized in that: in the step (6), the reaction conditions of the third reaction part are as follows: the temperature is 60-80 ℃, the pressure is 0-5MPa, and the ratio of the acid solution to the soapstock or the oil residue is 3-7: 1.

Technical Field

The invention relates to a combined method for continuously producing acidified oil, in particular to a method for continuously producing acidified oil by taking soapstock or oil foot as a raw material.

Background

The soapstock or the oil residue is leftovers generated in crude oil refining, neutral oil, pigment and other impurities are mixed in the leftovers, the composition of the soapstock generated by different processes and different raw materials is different, the soapstock generally contains 60-70% of soap, 15-40% of neutral oil and 30-45% of water, and most of the soapstock or the oil residue obtained by taking animal oil as the raw material also contains phospholipid.

The soapstock can be acidified to prepare acidified oil, and the acidified oil can be used as a raw material for preparing biodiesel. The traditional method for preparing the acidified oil from the soapstock is to add sulfuric acid into the soapstock, convert soap and neutral oil in the soapstock into fatty acid, remove residual acid liquor by water washing, obtain the acidified oil after standing and layering, generate a large amount of acid-containing wastewater and waste gas in the production process, and threaten the health and safety of operators in the operation process.

The Chinese patent with the publication number of CN101565654A discloses a method for producing acidified oil by using oil residue and/or soapstock, and discloses a method for producing acidified oil by using CO₂Acidification of soapstock by dissolving in water to form carbonic acid, but this method is only suitable for processing phospholipid-free soapstock or oil soapstock with mild properties due to CO₂The carbonic acid formed in water is less acidic than phosphoric acid and therefore cannot be fully acidified by this method for the majority of soapstock or oil stocks containing phospholipids.

Disclosure of Invention

In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a combined method for continuously producing the acidified oil, which solves the problem of secondary pollution in the traditional process, solves the problem of large wastewater amount and difficult treatment in the traditional process, solves the problem of difficult subsequent processing of the acidified oil, and has practical economic significance and environmental protection significance.

The purpose of the invention is realized by the following technical scheme: a combined continuous production method of acidified oil comprises the following steps:

(1) in the raw material mixing part, the soapstock or the oil foot is fully mixed with a certain proportion of water, and is pressurized by a pump and heated to 60-120 ℃, and then is mixed with acid gas and sent to the first reaction part;

(2) in the first reaction part, the acid gas is dissolved in water to form acid liquor, the acid liquor stays for 2 to 8 hours under the conditions that the pressure is 0 to 15Mpa and the temperature is 60 to 120 ℃, and the weight ratio of water to soapstock or oil stock is 0.5 to 3.0: 1, continuously reacting soapstock or oil residue with the acid liquor to obtain a first reaction product;

(3) in the first separation part, the first reaction product completes three-phase separation of oil, water and gas to obtain first separated gas, a first water phase and a first oil phase, the first separated gas is discharged to a torch system for incineration, the first water phase is discharged to a sewage treatment system for treatment, and the first oil phase is sent to the second reaction part;

(4) in the second reaction part, supplementing water and acid gas into the first oil phase, and staying for 1-5h under the conditions of 0-15MPa of pressure and 60-120 ℃ of temperature, wherein the weight ratio of water to soapstock or oil stock is 0.5-3:1, continuously reacting the first oil phase with acid liquor to obtain a second reaction product;

(5) in the second separation part, the second reaction product is separated into a second separation gas, a second oil phase, a phospholipid-containing soapstock or oil foot and a second water phase, the second separation gas returns to the first reaction part for recycling, the second oil phase is sent out as a non-phosphorylated oil product, the second water phase returns to the first reaction part for water supplement of the first reaction part, and the phospholipid-containing soapstock or oil foot is sent to a third reaction part; (6) in the third reaction part, after the phosphate-containing soapstock or oil foot is mixed with a certain proportion of 30-40% strong acid aqueous solution by mass, the mixture continuously reacts under the conditions that the pressure is 0-10MPa and the temperature is 50-100 ℃, and the obtained third reaction product is sent to the third separation part;

(7) in the third separation part, the third reaction product is separated into a third water phase containing strong acid salt crystals and a third oil phase containing partial acid liquor, the third water phase containing the strong acid salt crystals is discharged to a sewage treatment system, and the third oil phase containing partial acid liquor is sent to a fourth separation part;

(8) and in the fourth separation part, the third oil phase containing partial acid liquid is separated into phospholipid-containing acidified oil, vegetable asphalt and an acid-containing water phase, the acid-containing water phase returns to the third reaction part for recycling, and at least one part of the phospholipid-containing acidified oil returns to the third reaction part to be mixed with the phospholipid-containing soapstock or oil stock.

Preferably, in the step (2), the reaction conditions of the first reaction part are as follows: the temperature is 80-110 ℃, the pressure is 2.0-8.0MPa, the retention time is 3-5h, and the ratio of water to soapstock or oil residue is 1-2.5: 1.

preferably, in the step (4), the reaction conditions of the second reaction part are as follows: the temperature is 80-110 ℃, the pressure is 2.0-8.0MPa, the retention time is 2-3 hours, and the ratio of water to soapstock or oil residue is 1-2.5: 1.

preferably, in the step (6), the reaction conditions of the third reaction part are as follows: the temperature is 60-80 ℃, the pressure is 0-5MPa, and the ratio of the acid solution to the soapstock or the oil residue is 3-7: 1.

the invention has the beneficial effects that: the method adopts a weak acid and strong acid combined acidification method, utilizes the characteristic that the acidity of the weak acid is weaker than that of phosphoric acid, firstly uses the weak acid to carry out acidification and separation to obtain phospholipid-free acidified oil, and then uses the strong acid to carry out acidification and separation to obtain the residual phospholipid-containing acidified oil, so that the discharge of waste liquid containing the strong acid can be reduced, the burden of sewage treatment is greatly reduced, and high-quality acidified oil without phospholipid can be obtained, and convenience is provided for subsequent processing of the acidified oil.

Drawings

FIG. 1 is a schematic flow diagram of the present invention.

Detailed Description

For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and the accompanying fig. 1, and the description of the embodiments is not intended to limit the present invention.

The compositions or concentrations or amounts or yields of the components described herein are weight basis values unless otherwise specified.

The soapstock or the oil foot are leftovers generated in the refining of the crude oil, wherein impurities such as neutral oil, pigment and the like are mixed in the leftovers, the composition of the soapstock generated by different processes and different raw materials is different, the soapstock generally contains 60-70% of soap, 15-40% of neutral oil and 30-45% of water, and most of the soapstock or the oil foot obtained by taking the animal oil as the raw material contains phospholipid.

The acid gas refers to gas which can be dissolved in water to generate corresponding acid liquor,may be CO-containing₂Mixed gases of gases or containing SO₂Mixed gas of gases or containing H₂And S gas mixture.

The weak acid in the present invention refers to an acid having a weaker acidity than phosphoric acid, such as carbonic acid, sulfurous acid, and hydrosulfuric acid.

The strong acid in the invention refers to acids with stronger acidity than phosphoric acid, such as hydrochloric acid, sulfuric acid, nitric acid and the like.

Referring to fig. 1, the combined continuous production method of the acidified oil of the invention comprises the following steps:

(1) in the raw material mixing part, the soapstock or the oil residue is mixed with the second water phase from the second separation part, and after pressurizing and heating to 60-120 ℃ by a pump, the soapstock or the oil residue is mixed with the acid gas and sent to the first reaction part.

(2) In the first reaction part, the acid gas is dissolved in water to form acid liquor, the acid liquor stays for 2 to 8 hours under the conditions that the pressure is 0 to 15Mpa and the temperature is 60 to 120 ℃, the ratio of water to soapstock or oil stock is 0.5 to 3:1, and the soapstock or oil stock and the acid liquor continuously react to obtain a first reaction product; the reaction conditions in the first reaction section are preferably: the temperature is 80-110 ℃, the pressure is 2.0-8.0MPa, the retention time is 3-5 hours, and the ratio of water to soapstock or oil residue is 1-2.5: 1.

(3) In the first separation part, the first reaction product completes three-phase separation of oil, water and gas to obtain first separated gas, a first water phase and a first oil phase, the first separated gas is discharged to a torch system for incineration, the first water phase is discharged to a sewage treatment system for treatment, and the first oil phase is sent to the second reaction part.

The first separation section is operated at a pressure of the first reaction section minus the actual pressure drop.

(4) Supplementing water and acid gas into the first oil phase in a second reaction part, and staying for 1-5h under the conditions that the pressure is 0-15MPa and the temperature is 60-120 ℃, wherein the ratio of water to soapstock or oil stock is 0.5-3:1, and the first oil phase continuously reacts with acid liquor to obtain a second reaction product; the reaction conditions in the second reaction section are preferably: the temperature is 80-110 ℃, the pressure is 2.0-8.0MPa, the retention time is 2-3 hours, and the ratio of water to soapstock or oil residue is 1-2.5: 1; typically, acidification of 70-90% of the soapstock or oil bottoms will be accomplished after the first reaction section and the second reaction section.

The purpose of the first and second reaction sections is to convert the soapstock or oil bottoms of the starting material, which are mostly free of phospholipids, into an acidified oil, reducing the consumption of strong acids during the subsequent acidification of the phospholipid-containing soapstock or oil bottoms, so that in the first and second reaction sections typically more than 80% conversion of the phospholipid-free soapstock or oil bottoms, preferably more than 90% conversion of the phospholipid-free soapstock or oil bottoms, will be achieved.

(5) In the second separation part, the second reaction product is separated into a second separation gas, a second oil phase, a phospholipid-containing soapstock or oil foot and a second water phase, the second separation gas returns to the first reaction part for recycling, the second oil phase is sent out as a non-phosphorylated oil product, the second water phase returns to the first reaction part for water supplement of the first reaction part, and the phospholipid-containing soapstock or oil foot is sent to the third reaction part.

The second separation section is operated at a pressure of the second reaction section minus the actual pressure drop.

(6) In the third reaction part, after the phosphate-containing soapstock or oil foot is mixed with a strong acid aqueous solution with a mass fraction of 30-40% in a certain proportion, the mixture continuously reacts under the conditions that the pressure is 0-10MPa and the temperature is 50-100 ℃, and a reaction product is sent to the third separation part; the operating conditions of the third reaction section are preferably: the temperature is 60-80 ℃, the pressure is 0-5MPa, and the ratio of the acid solution to the soapstock or the oil residue is 3-7: 1.

(7) In the third separation part, the third reaction product is separated into a third water phase containing strong acid salt crystals and a third oil phase containing the acid solution, the third water phase containing the strong acid salt crystals is discharged to a sewage treatment system, and the third oil phase containing the acid solution is sent to the fourth separation part.

(8) And in the fourth separation part, the third oil phase of the acid-containing liquid is separated into phospholipid-containing acidified oil, vegetable asphalt and acid liquid, the acid liquid returns to the third reaction part for recycling, and at least one part of the phospholipid-containing acidified oil returns to the third reaction part as circulating oil to be mixed with the phospholipid-containing soapstock or oil stock.

And the phospholipid-containing acidic oil separated by the fourth separation part is sent out and then is stored separately.

The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.