CN1520901A - Application method of chemical industry by-products including organic acid - Google Patents
Application method of chemical industry by-products including organic acid Download PDFInfo
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Abstract
The application process of chemical side product containing organic acid includes well mixing hydrocarbon oil with chemical side product containing organic acid and water injecting demulsifier to make metal in hydrocarbon oil produce water soluble compound dissolved in water; and oil-water separating to eliminate metal from hydrocarbon oil. Meanwhile, the amount of the side product is 0.5-10 times total calcium molar number in hydrocarbon oil, the amount of water is 3-50 % of hydrocarbon oil volume, the oil-water mixing time is 0.5 sec to 10 min and the mixing temperature is 30-150 deg.c. The process of applying chemical side product directly in demetalizing hydrocarbon oil has low cost, simple operation and easy industrial application, can improve the quality of hydrocarbon oil obviously.
Description
Technical field
The present invention relates to contain the application method of organic acid chemical industry by product.
Technical background
In the method for industrial production hexanolactam, most is raw material with benzene, prepares through operations such as benzene hydrogenation, cyclohexane oxidation, pimelinketone oximate, rearrangement of cyclohexanone-oxime.The product of cyclohexane oxidation also has a considerable amount of organic acids, organic acid acetic compounds except pimelinketone, hexalin.In order to remove organic acid and the organic acid acetic in the deoxidation liquid, add in the sodium hydroxide solution usually and saponification, make system become alkalescence by acidity.Under alkaline condition, the profit two phase stratification: a large amount of unreacted hexanaphthenes reclaim with reacting pimelinketone, hexalin and the aqueous phase separation that generates; And organic acid sodium salt that acidic by-products such as organic acid and sodium hydroxide reaction generate and not separated organic ester ketone, polymkeric substance etc. enter water, form saponification waste liquid.
Saponification waste liquid is a kind of brownish black thick liquid, the strong impulse stink is arranged.Its composition is also different according to the difference of cyclohexane oxidation production technique, but generally all is that a few class materials such as sodium hydroxide, organic monoprotic acid, organic dibasic acid, organic ester ketone, polymkeric substance and water are formed.Wherein organic acid and sodium hydroxide reaction back exists with the form of organic acid sodium salt.Except a large amount of water, sodium hydroxide, total organic content reaches 23-30% in the saponification waste liquid.Organic acids such as butyric acid, valeric acid, caproic acid and hexanodioic acid most importantly in organism.Organic monacid content reaches 10-11% usually, is mainly butyric acid, valeric acid, caproic acid, and other has a spot of acetate, propionic acid, enanthic acid.The content of organic dibasic acid is mainly Succinic Acid, pentanedioic acid and hexanodioic acid usually at 1-5%, and other has a spot of pimelic acid.
Neutralisation is one of main method of handling both at home and abroad saponification waste liquid at present, promptly with sulfuric acid or nitric acid neutralizing treatment saponification waste liquid, makes organic acid sodium salt under acidification, forms the water that contains inorganic salt and contains the organic acid oil phase.Through the profit layering, separate obtaining containing organic acid saponified oil (being commonly called as black acid liquid).The content of the organic-unit's acid in the saponified oil reaches 35-50% usually, is mainly butyric acid, valeric acid, caproic acid, and other has a spot of acetate, propionic acid, enanthic acid; The content of organic dibasic acid is mainly Succinic Acid, pentanedioic acid and hexanodioic acid usually at 4-25%, and other has a spot of pimelic acid.Also contain organism such as organic ester ketone, polymkeric substance in addition in the saponified oil, total content is about 30-46%.Organic ester ketone is along with cyclohexane oxidation processing condition difference, and it is bigger to form variation, mainly contains tens kinds of compounds such as butyrolactone, cyclopentanone, cyclopentenes-1-ketone, cyclohexyl butyrate.Polymer class is mainly polyacrylic acid, polybutene acid, polypenthylene acid and Ester thereof etc.
The quantity discharged of saponification waste liquid, be generally 0.5-0.7 times of the caprolactam product amount, and adopt the amount of the saponification waste liquid of neutralisation processing to account for 1/3rd of saponification waste liquid total release, but at present except that the small amounts of soap carburetion can be utilized, most of fuel that is used as is burnt, and causes the serious waste of resource.
In addition, chemical industry by product, i.e. mixing acid in the Industrial processes of hexanodioic acid, have also been produced.In traditional Production Processes of Adipic Acid, or make starting raw material through producing cyclohexane by adding hydrogen with benzene, be reoxidised into hexalin and pimelinketone (KA oil), or make raw material with phenol and generate hexalin and pimelinketone (or KA oil), or directly generate hexalin and pimelinketone (KA oil) with cyclohexane give oxidation raw material through hydrogenation.Become hexanodioic acid with nitric acid oxidation KA oil at last.Improving although its production technique has experienced repeatedly, is that the nitric acid oxidation method of raw material remains one of technology of producing hexanodioic acid with hexalin/pimelinketone.Adopt this method, except that making hexanodioic acid, hexalin and pimelinketone also can be degraded to pentanedioic acid and the Succinic Acid that lacks one or two carbon atom than raw material.When the nitric acid oxidation product is concentrated with crystallization, obtain rough hexanodioic acid, be further purified then adipic acid product.Contain pentanedioic acid in the mother liquor after the crystallization, the mixing by product of Succinic Acid and hexanodioic acid, the about 33-34% of mixed dibasic acid total content in the mother liquor, all the other are water.Wherein contain hexanodioic acid 15-25% in the mixed dibasic acid, pentanedioic acid 50-60%, Succinic Acid 15-25%.The heating of diprotic acid mixed solution used vapour through triple effect evaporation, is reclaimed and is obtained the solid mixed dibasic acid.
The separation of mixed dibasic acid is difficulty very, and prior art does not still have effective separation method so far.
Summary of the invention
The object of the present invention is to provide a kind of organic acid chemical industry by product that will contain to be used for the demetallated method of hydrocarbon ils.
The application method that contains organic acid chemical industry by product provided by the invention comprises: with hydrocarbon ils with contain organic acid chemical industry by product, water filling and emulsion splitter thorough mixing, make the metal in the hydrocarbon ils generate water miscible title complex, be dissolved in the water, reach the purpose that removes metals in hydrocarbon oil by oily water separation.
Said chemical industry by product can be the saponified oil that obtains after the saponification waste liquid acidifying in the caprolactam production process, also can be the solid mixed dibasic acid that the chemical plant produces by-product in the adipic acid process.Wherein the saponified oil composition is mainly C
2-C
7Saturated monocarboxylic acid or di-carboxylic acid, monacid content is generally 35-50%, is mainly butyric acid, valeric acid, caproic acid, other has a spot of acetate, propionic acid, enanthic acid; The content of diprotic acid is mainly Succinic Acid, pentanedioic acid and hexanodioic acid usually at 4-25%, and other has a spot of pimelic acid, and all the other organic content are 30-46%.The solid mixed dibasic acid of industrial production hexanodioic acid institute by-product is mainly by C
4-C
6Diprotic acid form hexanodioic acid 15-25% wherein, pentanedioic acid 50-60%, Succinic Acid 15-25%.Said by product has good complex ability to the metals such as calcium, magnesium and iron of the organic bound state in the hydrocarbon ils oil, can be used as metal remover and uses, and is particularly suitable for deliming, especially is non-porphyrin calcium cpd.
Said hydrocarbon ils can be crude oil, shale oil and residual oil etc. by crude oil derived other hydrocarbon ils that goes out.
When said by product uses as metal remover, with the inverse of contained carboxylate radical mole number in this kind by product of unit mass molar mass as this metal remover, its consumption be total calcium mole number in the hydrocarbon ils 0.5-10 doubly, be preferably 1-5 doubly.Before the injecting, metal remover can add hydrocarbon ils earlier and mix with it, can also be made into the aqueous solution and add hydrocarbon ils again and mix with it.Preferably be made into the aqueous solution earlier, concentration of aqueous solution is at 10-40%.Total Water is the 3-50% of hydrocarbon ils volume, preferred 5-20%.The profit mixing time was generally 0.5 second-10 minutes, preferred 1 second-2 minutes.Mixing temperature changes with the density and the viscosity of hydrocarbon ils pan feeding, and density is high more, and viscosity is big more, and then mixing temperature is high more, otherwise then can carry out being low to moderate under the room temperature, is generally 30-150 ℃, preferred 60-130 ℃.
The emulsion splitter that the inventive method is used can be selected according to the kind of hydrocarbon ils, can be used as auxiliary products and buys from the producer that sells hydrocarbon ils.Can be single emulsion splitter or composite demulsifying agent, as BP2040, FC9301, NS-9906 etc., consumption be the 1-100ppm of hydrocarbon ils weight, and the effect of emulsion splitter is to promote oily water separation.
The inventive method can be carried out in the conventional demineralising process of refinery, can realize on electric desalting apparatus in the actually operating, and decalcification is finished with desalination, dehydration.The single stage desalting device be can adopt, secondary or three grades of desalting plants also can be adopted.
The inventive method can be applicable to contain any hydrocarbon ils of super allowance calcium.
The inventive method is directly used in the hydrocarbon ils demetalization with the chemical industry by product, and is with low cost, simple to operate, is easy to industrialization, can the hydrocarbon ils quality be significantly improved by this method, has the obvious economic benefit that gets.The inventive method is a raw material with the chemical industry by product simultaneously, turns waste into wealth, and saves resource, has important social benefit.
Embodiment
Embodiment 1
The by product (containing hexanodioic acid 50.5%, pentanedioic acid 39.0%, succinic anhydride class 7.3% and ketone and amides 3.2%) that adopts certain chemical plant to produce hexanodioic acid carries out decalcification as decalcifying agent.Experiment is taken from Lanzhou factory of petrochemical refining with stock oil, is the mixing oil (calcic: 45ppm) of North SinKiang, Xinjiang crude oil and South Sinkiang crude oil.Emulsion splitter NS-9906 and decalcifying agent are added water filling, emulsion splitter dosage 50ppm, injection rate 10% by certain agent/calcium ratio; The crude oil that will be preheated to 60 ℃ in agitator mixed for 10 seconds with water, made the profit thorough mixing, and oil-water mixture is poured the cone-shaped glass jar into, put tapered shaped can into DP-II type electric desalting instrument, desalination instrument electric-force gradient 200v/cm, 80 ℃ of temperature, 1 hour time.After the oily water separation, get and take off back oil sample using plasma emission spectrometer (ICI/AES) mensuration calcium contents.Table 1 is the decalcification result.
Table 1
| Agent/calcium mol ratio | Take off back crude oil calcium contents, ppm | The calcium decreasing ratio, % |
| ????1.5∶1 | ????7.7 | ????82.9 |
| ????2.0∶1 | ????4.5 | ????90.0 |
| ????2.5∶1 | ????2.1 | ????95.3 |
Embodiment 2
The by product (containing hexanodioic acid 50.5%, pentanedioic acid 39.0%, succinic anhydride class 7.3% and ketone and amides 3.2%) that adopts certain chemical plant to produce hexanodioic acid carries out decalcification as decalcifying agent.In the present embodiment, experiment is Kelamayi, an Xinjiang Jiu Qu viscous crude with oil, calcium contents 240ppm, emulsion splitter FC9301, add-on 50ppm, injection rate 10%.The crude oil preheating temperature is 90 ℃, and temperature is 90 ℃ in the electric desalting instrument.Experimental technique is identical with embodiment 1.Table 2 is an experimental result.
Table 2
| The crude oil type | Agent/calcium mol ratio | Take off calcium contents in the crude oil of back, ppm | The decalcification rate, % |
| Kelamayi, Xinjiang Jiu Qu viscous crude, calcium contents 240ppm | ????1.0∶1 | ????121.2 | ????49.5 |
| ????1.5∶1 | ????84.2 | ????64.9 | |
| ????2.0∶1 | ????80.2 | ????66.5 | |
| ????2.5∶1 | ????66.5 | ????72.3 | |
| ????3.0∶1 | ????33.8 | ????85.9 | |
| ????3.5∶1 | ????16.3 | ????93.2 | |
| Kelamayi Jiu Qu viscous crude and kerosene are with 7: 3 mixing oil, calcium contents 152ppm | ????1.5∶1 | ????47.6 | ????68.9 |
| ????2.0∶1 | ????16.4 | ????89.2 | |
| ????2.5∶1 | ????6.4 | ????95.8 |
Embodiment 3
Adopt the by product (containing monoprotic acid 45%, diprotic acid 25% and other organism 30%) of certain chemical plant industrial production hexanolactam to carry out decalcification as metal remover, in the present embodiment, experiment is Kelamayi, an Xinjiang Jiu Qu viscous crude with crude oil, emulsion splitter FC9301, add-on 50ppm, injection rate 10%.The crude oil preheating temperature is 100～110 ℃, and temperature is 90 ℃ in the electric desalting instrument.Experimental technique is identical with embodiment 1.Table 3 is an experimental result.
Table 3
| Agent/calcium mol ratio | Take off back crude oil calcium contents, ppm | The calcium decreasing ratio, % |
| ????2.0 | ????107.0 | ????55.4 |
| ????2.5 | ????75.1 | ????68.7 |
| ????3.0 | ????47.0 | ????80.4 |
| ????3.5 | ????28.8 | ????88.0 |
| ????4.0 | ????5.0 | ????97.9 |
Claims (10)
1. the application method that contains organic acid chemical industry by product, comprise: with hydrocarbon ils with contain organic acid chemical industry by product, water filling and emulsion splitter thorough mixing, make the metal in the hydrocarbon ils generate water miscible title complex, be dissolved in the water, by oily water separation, remove metals in hydrocarbon oil, wherein in the by product with unit mass the inverse of contained carboxylate radical mole number as the molar mass of by product, the consumption of by product is 0.5-10 a times of total calcium mole number in the hydrocarbon ils, the water yield is the 3-50% of hydrocarbon ils volume, the profit mixing time-as be 0.5 second-10 minutes, mixing temperature is 30-150 ℃.
2. according to the described application method of claim 1, it is characterized in that said chemical industry by product is the C that contains that obtains after the saponification waste liquid acidifying in the caprolactam production process
2-C
7Saturated monoprotic acid and the saponified oil of diprotic acid.
3. according to claim 1 or 2 described application methodes, it is characterized in that, monacid content 35-50% in the saponified oil, the content 4-25% of diprotic acid, all the other organic content are 30-46%.
4. according to the described application method of claim 1, it is characterized in that said chemical industry by product is the C that the chemical plant produces by-product in the hexanodioic acid process
4-C
6Mixed dibasic acid.
5. according to claim 1 or 4 described application methodes, it is characterized in that, in the mixed dibasic acid, hexanodioic acid 15-25%, pentanedioic acid 50-60%, Succinic Acid 15-25%.
6. according to the described application method of claim 1, it is characterized in that the consumption of by product is 1-5 a times of total calcium mole number in the hydrocarbon ils.
7. according to the described application method of claim 1, it is characterized in that the water yield is the 5-20% of hydrocarbon ils volume.
8. according to the described application method of claim 1, it is characterized in that profit mixing time 1 second-2 minutes.
9. according to the described application method of claim 1, it is characterized in that mixing temperature is 60-130 ℃.
10. according to the described application method of claim 1, it is characterized in that the emulsion splitter consumption is the 1-100ppm of hydrocarbon ils weight.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03102265 CN1272080C (en) | 2003-01-30 | 2003-01-30 | Application method of chemical industry by-products including organic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191078A (en) * | 2010-03-04 | 2011-09-21 | 中国石油化工股份有限公司 | Method for lowering corrosivity of acid-containing hydrocarbon oil |
| CN104449811A (en) * | 2013-09-23 | 2015-03-25 | 中国石油化工股份有限公司 | Demetalization method for hydrocarbon oil |
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2003
- 2003-01-30 CN CN 03102265 patent/CN1272080C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191078A (en) * | 2010-03-04 | 2011-09-21 | 中国石油化工股份有限公司 | Method for lowering corrosivity of acid-containing hydrocarbon oil |
| CN102191078B (en) * | 2010-03-04 | 2013-09-25 | 中国石油化工股份有限公司 | Method for lowering corrosivity of acid-containing hydrocarbon oil |
| CN104449811A (en) * | 2013-09-23 | 2015-03-25 | 中国石油化工股份有限公司 | Demetalization method for hydrocarbon oil |
| CN104449811B (en) * | 2013-09-23 | 2016-03-02 | 中国石油化工股份有限公司 | A kind of Demetalization method by hydrocarbon oil |
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| CN1272080C (en) | 2006-08-30 |
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