CN1272080C - 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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- CN1272080C CN1272080C CN 03102265 CN03102265A CN1272080C CN 1272080 C CN1272080 C CN 1272080C CN 03102265 CN03102265 CN 03102265 CN 03102265 A CN03102265 A CN 03102265A CN 1272080 C CN1272080 C CN 1272080C
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Abstract
The present invention relates to an application method for a chemical industry side product containing organic acid, which comprises the steps that water is injected into hydrocarbon oil and the chemical industry side product containing the organic acid, the hydrocarbon oil and the chemical industry side product containing the organic acid are fully mixed with a deemulsifying agent, metal in the hydrocarbon oil generates a water-soluble coordination compound, and the water-soluble coordination compound is dissolved in the water; the metal in the hydrocarbon oil is eliminated by the separation of the water and the oil, wherein the ciprocal value of the mole number of a carboxylate radical in the side product of unit mass is used as the molar mass of the side product; and the dosage of the side product is 0.5 to 10 times of the total calcium mole number of the hydrocarbon oil, water quantity is 3 to 50% of the volume of the hydrocarbon oil, the mixing time of the oil and the water is from 0.5 second to 10 minutes, and mixing temperature is from 30 to 150 DEG C. The chemical industry side product is directly used for the demetalization of the hydrocarbon oil by the method, and the method has the advantages of low cost, simple operation and easy industrialization, obviously improves the quality of hydrocarbon oil processed by the method, and has obvious economic benefit. Simultaneously, the method uses the side product as raw materials, and the wastes are changed into valuables for saving sources; therefore, significant social benefit is achieved.
Description
Technical field
The present invention relates to contain the application process of organic acid chemical industry accessory substance.
Technical background
In the method for industrial production caprolactam, most is raw material with benzene, prepares through operations such as benzene hydrogenation, cyclohexane oxidation, cyclohexanone oximate, rearrangement of cyclohexanone-oxime.The product of cyclohexane oxidation also has a considerable amount of organic acids, organic acid esters compounds except cyclohexanone, cyclohexanol.In order to remove organic acid and the organic acid esters in the deoxidation liquid, add in the sodium hydroxide solution usually and saponification, make system become alkalescence by acidity.Under alkali condition, the profit two phase stratification: a large amount of unreacted cyclohexanes reclaim with reacting cyclohexanone, cyclohexanol and the aqueous phase separation that generates; And organic acid sodium salt that acidic by-products such as organic acid and NaOH reaction generate and not separated organic ester ketone, polymer 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 technology, but generally all is that a few class materials such as NaOH, organic monoacid, organic dibasic acid, organic ester ketone, polymer and water are formed.Wherein organic acid and NaOH reaction back exists with the form of organic acid sodium salt.Except a large amount of water, NaOH, total organic content reaches 23-30% in the saponification waste liquid.Organic acids such as butyric acid, valeric acid, caproic acid and adipic acid most importantly in organic matter.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, glutaric acid and adipic 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 neutralisation treatment saponification waste liquid, makes organic acid sodium salt under acidization, forms the water that contains inorganic salts 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).Organic monacid content 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, glutaric acid and adipic acid usually at 4-25%, and other has a spot of pimelic acid.Also contain organic matters such as organic ester ketone, polymer in addition in the saponified oil, total content is about 30-46%.Organic ester ketone is along with cyclohexane oxidation process conditions difference, and it is bigger to form variation, mainly contains tens kinds of compounds such as butyrolactone, cyclopentanone, cyclopentene-1-ketone, cyclohexyl butyrate.Polymer class is mainly polyacrylic acid, polybutene acid, polypenthylene acid and Ester thereof etc.
The discharge capacity 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 accessory substance, i.e. mixed acid in the industrial processes of adipic acid, have also been produced.In traditional Production Processes of Adipic Acid, or make initiation material through producing cyclohexane by adding hydrogen with benzene, be reoxidised into cyclohexanol and cyclohexanone (KA oil), or make raw material with phenol and generate cyclohexanol and cyclohexanone (or KA oil), or directly generate cyclohexanol and cyclohexanone (KA oil) with cyclohexane give oxidation raw material through hydrogenation.Become adipic acid with nitric acid oxidation KA oil at last.Improving although its production technology has experienced repeatedly, is that the nitric acid oxidation method of raw material remains one of technology of producing adipic acid with cyclohexanol/cyclohexanone.Adopt this method, except that making adipic acid, cyclohexanol and cyclohexanone also can be degraded to glutaric 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 adipic acid, be further purified then adipic acid product.Contain glutaric acid in the mother liquor after the crystallization, the mixing accessory substance of succinic acid and adipic acid, the about 33-34% of mixed dibasic acid total content in the mother liquor, all the other are water.Wherein contain adipic acid 15-25% in the mixed dibasic acid, glutaric acid 50-60%, succinic acid 15-25%.The heating of binary acid mixed liquor 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 accessory substance that will contain to be used for the demetallated method of hydrocarbon ils.
The application process that contains organic acid chemical industry accessory substance provided by the invention comprises: with hydrocarbon ils with contain organic acid chemical industry accessory substance, water filling and demulsifier and fully mix, make the metal in the hydrocarbon ils generate water miscible complex, be dissolved in the water, reach the purpose that removes metals in hydrocarbon oil by water-oil separating.
Said chemical industry accessory substance 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 dicarboxylic acids, 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 binary acid is mainly succinic acid, glutaric acid and adipic 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 adipic acid institute by-product is mainly by C
4-C
6Binary acid form adipic acid 15-25% wherein, glutaric acid 50-60%, succinic acid 15-25%.Said accessory substance has good complexing power 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 compound.
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 accessory substance uses as metal remover, with the inverse of contained carboxylate radical molal quantity in this kind accessory substance of unit mass molal weight as this metal remover, its consumption be total calcium molal quantity 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 incorporation 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 demulsifier 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 demulsifier or composite demulsifying agent, as BP2040, FC9301, NS-9906 etc., consumption be the 1-100ppm of hydrocarbon ils weight, and the effect of demulsifier is to promote water-oil separating.
The inventive method can be carried out in the conventional desalination processes of oil plant, can realize on electric desalting apparatus in the practical operation, and decalcification is finished with desalination, dehydration.The single stage desalting device be can adopt, secondary or three grades of desalters 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 accessory substance, 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 accessory substance simultaneously, turns waste into wealth, and saves resource, has important social benefit.
The specific embodiment
Embodiment 1
The accessory substance (containing adipic acid 50.5%, glutaric acid 39.0%, succinic anhydride class 7.3% and ketone and amide-type 3.2%) that adopts certain chemical plant to produce adipic acid carries out decalcification as decalcifying agent.Experiment is taken from Lanzhou factory of petrochemical refining with feedstock oil, is the miscella (calcic: 45ppm) of North SinKiang, Xinjiang crude oil and South Sinkiang crude oil.Demulsifier NS-9906 and decalcifying agent are added water filling, demulsifier 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, and profit is fully mixed, and oil water mixture is poured the cone-shaped glass jar into, put tapered shaped can into DP-II type electro-desalting instrument, desalination instrument electric-force gradient 200v/cm, 80 ℃ of temperature, 1 hour time.After the water-oil separating, get and take off back oil sample using plasma emission spectrometer (ICI/AES) mensuration calcium content.Table 1 is the decalcification result.
Table 1
| Agent/calcium mol ratio | Take off back crude oil calcium content, ppm | The calcium removal efficiency, % |
| 1.5∶1 | 7.7 | 82.9 |
| 2.0∶1 | 4.5 | 90.0 |
| 2.5∶1 | 2.1 | 95.3 |
Embodiment 2
The accessory substance (containing adipic acid 50.5%, glutaric acid 39.0%, succinic anhydride class 7.3% and ketone and amide-type 3.2%) that adopts certain chemical plant to produce adipic acid carries out decalcification as decalcifying agent.In the present embodiment, experiment is Kelamayi, an Xinjiang Jiu Qu viscous crude with oil, calcium content 240ppm, demulsifier FC9301, addition 50ppm, injection rate 10%.The crude oil preheat temperature is 90 ℃, and temperature is 90 ℃ in the electro-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 content in the crude oil of back, ppm | The decalcification rate, % |
| Kelamayi, Xinjiang Jiu Qu viscous crude, calcium content 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 miscella, calcium content 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 accessory substance (containing monoacid 45%, binary acid 25% and other organic matter 30%) of certain chemical plant industrial production caprolactam to carry out decalcification as metal remover, in the present embodiment, experiment is Kelamayi, an Xinjiang Jiu Qu viscous crude with crude oil, demulsifier FC9301, addition 50ppm, injection rate 10%.The crude oil preheat temperature is 100～110 ℃, and temperature is 90 ℃ in the electro-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 content, ppm | The calcium removal efficiency, % |
| 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 (7)
1. the application process that contains organic acid chemical industry accessory substance, comprise: with hydrocarbon ils with contain organic acid chemical industry accessory substance, water and demulsifier fully mix, make the metal in the hydrocarbon ils generate water miscible complex, be dissolved in the water, by water-oil separating, remove metals in hydrocarbon oil, wherein in the accessory substance with unit mass the inverse of contained carboxylate radical molal quantity as the molal weight of accessory substance, the consumption of accessory substance is 0.5-10 a times of total calcium molal quantity in the hydrocarbon ils, the water yield is the 3-50% of hydrocarbon ils volume, the demulsifier consumption is the 1-100ppm of hydrocarbon ils weight, the profit incorporation time is 0.5 second-10 minutes, mixing temperature is 30-150 ℃, and said chemical industry accessory substance is the C that contains that obtains after the saponification waste liquid acidifying in the caprolactam production process
2-C
7Saturated monoacid and the saponified oil of binary acid or the chemical plant C that produces by-product in the adipic acid process
4-C
6Mixed dibasic acid.
2. according to the described application process of claim 1, it is characterized in that, monacid content 35-50% in the saponified oil, the content 4-25% of binary acid, all the other organic content are 30-46%.
3. according to the described application process of claim 1, it is characterized in that, in the mixed dibasic acid, adipic acid 15-25%, glutaric acid 50-60%, succinic acid 15-25%.
4. according to the described application process of claim 1, it is characterized in that the consumption of accessory substance is 1-5 a times of total calcium molal quantity in the hydrocarbon ils.
5. according to the described application process of claim 1, it is characterized in that the water yield is the 5-20% of hydrocarbon ils volume.
6. according to the described application process of claim 1, it is characterized in that profit incorporation time 1 second-2 minutes.
7. according to the described application process of claim 1, it is characterized in that mixing temperature is 60-130 ℃.
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| 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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