CN109439362A - A kind of preparation method of the chloride shift agent for electric desalting apparatus - Google Patents
A kind of preparation method of the chloride shift agent for electric desalting apparatus Download PDFInfo
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- CN109439362A CN109439362A CN201811040628.9A CN201811040628A CN109439362A CN 109439362 A CN109439362 A CN 109439362A CN 201811040628 A CN201811040628 A CN 201811040628A CN 109439362 A CN109439362 A CN 109439362A
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- chloride
- quaternary amine
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
- C10G32/02—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by electric or magnetic means
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention discloses a kind of preparation methods of chloride shift agent for electric desalting apparatus, and organochlorine in crude oil is quickly converted as inorganic chlorine with achieving the purpose that realize.Quaternary amine is generated under solvent condition by tertiary amine and benzyl chloride, quaternary amine and sodium hydroxide generate quaternary amine alkali under the conditions of dehydrated alcohol, the ethanol solution of quaternary amine alkali is compounded with the aqueous solution of sodium hydroxide, obtains the heretofore described chloride shift agent for electric desalting apparatus.Chloride shift agent in the present invention is used for crude oil electric desalting process, can quickly and effectively convert inorganic chlorine for the organochlorine in crude oil, and then exhaust with desalted water.The problems such as chloride shift agent preparation cost is low, is convenient for industrial application, can effectively reduce chlorine corrosion, the blocking, catalyst poisoning of subsequent crude oil processing equipment.
Description
Technical field
The present invention relates to a kind of preparation methods of chloride shift agent for electric desalting apparatus, belong to catalyst field.
Background technique
Butter and organic chloride are the main sources of the chlorine in crude oil.Butter is mainly villaumite, packet
Include sodium chloride, magnesium chloride, calcium chloride etc..It is dissolved in a small amount of water that crude oil contains, or crude oil is distributed in suspended particulate, crystal
In.Crude oil salt content is down to 3mg/L after three-level electro-desalting processing, and inorganic chlorine, which is substantially all, to be removed, but refinery plate
Block cryogenic system and face the heat exchanger of hydrogen system reaction effluent there are still serious ammonium chloride salt crust and etching problem, this
Illustrate that organochlorine still remains in crude oil.Electro-desalting can not effectively remove organic chloride contained in crude oil, a small amount of organochlorine
It can be decomposed in crude oil processing and generate butter, bring low temperature position HCl corrosion and NH4The problems such as Cl salt crust,
It is reported that heating crude oil mistake can also be made even if the organochlorine of 1 μ g/g under saliferous is reduced to 3mg/L following situations after crude oil is de-
The HCl formed in journey doubles.Therefore the problem of organochlorine in crude oil becomes current urgent need to resolve, general control how to be controlled
In 1-3 μ g/g.
Since the chlorine atom electronegativity in organic chloride is stronger, so that coupled carbon atom shows positive electricity, therefore can
With the substance for selecting nucleophilicity strong compared with chlorine, chlorine is removed by nucleophilic substitution.Any reactant with unshared electron pair
Kind (lewis alkali) all can serve as nucleopilic reagent no matter it is neutral or electronegativity, select nucleophilicity stronger than chlorine
Nucleopilic reagent can remove the chlorine in oil product.Organic chlorohydrocarbon can be reacted with sodium hydroxide generates fatty alcohol and sodium chloride,
Fatty alcohol is dissolved in oil and stays in crude oil, and sodium chloride is soluble in water to be removed.There is no catalyst reaction speed very slow, if be added
Phase transfer catalyst can greatly speed up reaction speed.
When ASTM D4929 analyzes chlorinity in crude oil, inorganic chlorine is converted by organochlorine with xenyl sodium, principle is
Utilize the nucleophilicity of carbanion.Patent US H001143 is described using Cymag and sodium sulfocynanate as nucleopilic reagent, in diformazan
The method that organochlorine in hydrocarbons is removed in sulfoxide solvent, this method can remove most of chlorine therein.This method
Deficiency is that the water solubility of substitution product is bad, and part oil-soluble products stay in oil product, cause crude oil pollution.And react needs
These reagent prices of a large amount of dimethyl sulfoxide are expensive, toxicity is big.
Patent CN 201010299752.4, which is described, is removed chlorine in oil product by the alkylating of organic amine substance
Method, the principle of this method: lone pair electrons on nitrogen-atoms have nucleophilicity, and amine substance and organic chloride reaction generate
Quaternary ammonium salt removes chlorine in electric desalting apparatus, can achieve certain dechlorination effect.But alkylated reaction requires amine
Matter is excessive, and the oil-soluble of organic amine is fine, and so that excessive amine substance is difficult to the separation from oil causes oily phase nitrogen content to increase.
For 101899321 A of patent CN using the method for organochlorine in chlorine element removing transfer agent removing oil product, this method can
To reach preferable effect.The raw material of chloride shift agent includes: N, N dimethyl propane diamine, cetylamine polyoxyethylene poly-oxygen propylene aether,
Modified hydroxide beta-hydroxyethyl trimethylamine and decyl alcohol.Dechlorination principles are as follows: N, N dimethyl propane diamine is in modified hydroxide beta-hydroxyethyl
Under the catalytic action of trimethylamine, is acted on the organic chloride in crude oil and chlorine element is transferred to water phase, in cetylamine polyoxy second
Water-oil separating under alkene polyethenoxy ether and electric field action, so that chlorine element be removed from oily phase.This method effect is preferable, but phase
Transfer agent is expensive, and increases subsequent denitrification process burden.
To sum up, by converting inorganic chlorine for organochlorine in crude oil, exploitation is for different shape organochlorine conversion medicament
Prevent chlorine corrosion direction and the trend of crude oil processing.It therefore, is to realize that chlorine converts effective using the method for necleophilic reaction
Approach, select nucleophilicity it is moderate, easily with the nucleopilic reagent of separation of oil, develop that cheap, preparation method is simple, changing effect
Significant chloride shift agent is focus on research direction.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of chloride shift agent for electric desalting apparatus, pass through this method
The chloride shift agent of preparation is used for crude oil electric desalting process, can quickly and effectively convert inorganic chlorine for the organochlorine in crude oil, in turn
It is exhausted with desalted water.It is at low cost, it is convenient for industrial application, can effectively reduce chlorine corrosion, the blocking, catalysis of subsequent crude oil processing equipment
The problems such as agent is poisoned.
To achieve the above object, The technical solution adopted by the invention is as follows:
It is mutually constantly recycled between water phase by the phase transfer catalyst in chloride shift agent oily, by the organochlorine in crude oil
Compound is converted into inorganic chloride.The preparation of chloride shift agent is reacted in two steps: the first step, and parent occurs by benzyl chloride and tertiary amine
Core substitution reaction generates intermediate quaternary ammonium salt；Second step converts the stronger quaternary amine of the nucleophilic heart for quaternary ammonium salt using sodium hydroxide
Alkali.
A kind of preparation method of chloride shift agent for electric desalting apparatus of the present invention: by tertiary amine and benzyl chloride according to
Molar ratio 1:1 generates quaternary amine, quaternary amine and sodium hydroxide according to molar ratio 1:1~10 in dehydrated alcohol item under solvent condition
Quaternary amine alkali is generated under part, the ethanol solution of quaternary amine alkali is compounded with the aqueous solution of sodium hydroxide, is obtained for electric desalting apparatus
Chloride shift agent.
The tertiary amine includes one of trimethylamine, triethylamine, tripropyl amine (TPA), N- methyl-diethyl-amine.
The solvent is neutrality or micropolar, including one of ethyl alcohol, water, tetrahydrofuran.
Generate the reaction condition of quaternary ammonium salt are as follows: 10~80 DEG C of temperature, 10~30min of time.
The molar ratio of quaternary amine and sodium hydroxide is in 1:1~10.
Generate the reaction condition of quaternary amine alkali are as follows: 40~100 DEG C of temperature, 10~30min of time；
The ethanol solution mass percentage 1%-10% of the quaternary amine alkali.
The aqueous solution mass percentage 0.1-10% of the sodium hydroxide.
Chloride shift agent in the present invention is used for crude oil electric desalting process, and the chloride shift agent is applied to atmospheric and vacuum distillation dress
In electric desalting apparatus before setting, it is pumped into high voltage electric field with crude oil, can quickly and effectively convert nothing for the organochlorine in crude oil
Organochlorine in crude oil is converted inorganic salts by machine chlorine, chloride shift agent, and conversion ratio reaches 90% or more；Utilize organochlorine in crude oil
With organic chloride nucleophilic substitution occurs for electronegativity feature, together using nucleopilic reagent more stronger than chloride ion nucleophilicity
When, consisting of phase-transferring agent is introduced, the generation of nucleophilic substitution is accelerated, can quickly and effectively convert organochlorine in crude oil to inorganic
Chlorine；And then it is exhausted with desalted water.The chloride shift agent preparation cost is low, is convenient for industrial application, can effectively reduce subsequent crude oil
The problems such as chlorine corrosion of processing unit (plant), blocking, catalyst poisoning.
Specific embodiment
In order to realize the present invention technological means, creation characteristic, reach purpose and dechlorination effect is easy to understand, into
One step illustrates the present invention.In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available.
Method in following embodiments is unless otherwise instructed the conventional method of this field.
Embodiment 1:
Etoh solvent 500ml is weighed, the three-necked flask (1000ml) of blender, reflux condenser and thermometer is placed in
In, the successively benzyl chloride (126.58g) of additional proportion (molar ratio 1:1), trimethylamine (59.11g), starting stirring fills reactant
Divide mixing, 10 DEG C of water-bath temperature control, reaction time 30min, generates benzyltrimethylammonium chloride, solvent is evaporated off, obtains white crystal
Benzyltrimethylammonium chloride.By quaternary ammonium salt benzyltrimethylammonium chloride and sodium hydroxide in proportion 1:1 (molar ratio) be placed in it is anhydrous
In alcohol solvent, 40 DEG C of water-bath temperature control, it is stirred to react 10min, filters and steams solvent and obtain quaternary amine alkali benzyl trimethyl hydrogen-oxygen
Change ammonium.Finally by the ethanol solution of 1% quaternary amine alkali benzyltrimethylammonium hydroxide and 0.1% sodium hydrate aqueous solution 1:1 (matter
Amount ratio) compounding obtain chloride shift agent.
Embodiment 2:
Etoh solvent 500ml is weighed, the three-necked flask (1000ml) of blender, reflux condenser and thermometer is placed in
In, the successively benzyl chloride (126.58g) of additional proportion (molar ratio 1:1), triethylamine (101.19g), starting stirring makes reactant
It is sufficiently mixed, 45 DEG C of water-bath temperature control, reaction time 20min, generates benzyltriethylammoinium chloride, solvent is evaporated off, obtain white crystalline substance
Body benzyltriethylammoinium chloride.By quaternary ammonium salt benzyltriethylammoinium chloride, 1:1 (molar ratio) is placed in nothing in proportion with sodium hydroxide
In alcoholic solvent, 40 DEG C of water-bath temperature control, it is stirred to react 10min, filters and steams solvent and obtain quaternary amine alkali benzyl triethyl ammonium hydrogen
Amine-oxides.Finally by the ethanol solution of 1% quaternary amine alkali benzyltriethylammonium hydroxide and 0.1% sodium hydrate aqueous solution 1:1
(mass ratio) compounding obtains chloride shift agent.
Embodiment 3:
Etoh solvent 500ml is weighed, the three-necked flask (1000ml) of blender, reflux condenser and thermometer is placed in
In, the successively benzyl chloride (126.58g) of additional proportion (molar ratio 1:1), tripropyl amine (TPA) (143.27g), starting stirring makes reactant
It is sufficiently mixed, 80 DEG C of water-bath temperature control, reaction time 10min, generates benzyl tripropyl ammonium chloride, solvent is evaporated off, obtain white crystalline substance
Body benzyl tripropyl ammonium chloride.By quaternary ammonium salt benzyl tripropyl ammonium chloride, 1:1 (molar ratio) is placed in nothing in proportion with sodium hydroxide
In alcoholic solvent, 40 DEG C of water-bath temperature control, it is stirred to react 10min, filters and steams solvent and obtain quaternary amine alkali benzyl tripropyl hydrogen
Amine-oxides.Finally by the ethanol solution and 0.1% sodium hydrate aqueous solution 1:1 of 1% quaternary amine alkali benzyl tripropyl ammonium hydroxide
(mass ratio) compounding obtains chloride shift agent.
Embodiment 4:
Solvent deionized water 500ml is weighed, the three-necked flask of blender, reflux condenser and thermometer is placed in
In (1000ml), successively the benzyl chloride (126.58g) of additional proportion (molar ratio 1:1), N- methyl-diethyl-amine (116.2g), start
Stirring is sufficiently mixed reactant, 45 DEG C of water-bath temperature control, reaction time 30min, generates benzyl methyl diethylammonium chloride, is evaporated off
Solvent obtains white crystal benzyl methyl diethylammonium chloride.By quaternary ammonium salt benzyl methyl diethylammonium chloride and sodium hydroxide
1:1 (molar ratio) is placed in anhydrous ethanol solvent in proportion, 40 DEG C of water-bath temperature control, is stirred to react 10min, is filtered and steam solvent
Obtain quaternary amine alkali benzyl methyl diethyl ammonium hydroxide.Finally by the second of 1% quaternary amine alkali benzyl methyl diethyl ammonium hydroxide
Alcoholic solution compounds to obtain chloride shift agent with 0.1% sodium hydrate aqueous solution 1:1 (mass ratio).
Embodiment 5:
Solvents tetrahydrofurane 500ml is weighed, the three-necked flask of blender, reflux condenser and thermometer is placed in
In (1000ml), successively the benzyl chloride (126.58g) of additional proportion (molar ratio 1:1), triethylamine (101.19g), start stirring
It is sufficiently mixed reactant, 45 DEG C of water-bath temperature control, reaction time 20min, benzyltriethylammoinium chloride is generated, solvent is evaporated off, obtains
To white crystal benzyltriethylammoinium chloride.By quaternary ammonium salt benzyltriethylammoinium chloride and sodium hydroxide in proportion 1:1 (mole
Than) be placed in anhydrous ethanol solvent, 40 DEG C of water-bath temperature control, it is stirred to react 10min, filters and steams solvent and obtain quaternary amine alkali benzyl
Triethylammonium hydroxide.Finally by the ethanol solution of 1% quaternary amine alkali benzyltriethylammonium hydroxide and 0.1% sodium hydroxide water
Solution 1:1 (mass ratio) compounding obtains chloride shift agent.
Embodiment 6:
Etoh solvent 500ml is weighed, the three-necked flask (1000ml) of blender, reflux condenser and thermometer is placed in
In, the successively benzyl chloride (126.58g) of additional proportion (molar ratio 1:1), triethylamine (101.19g), starting stirring makes reactant
It is sufficiently mixed, 45 DEG C of water-bath temperature control, reaction time 20min, generates benzyltriethylammoinium chloride, solvent is evaporated off, obtain white crystalline substance
Body benzyltriethylammoinium chloride.By quaternary ammonium salt benzyltriethylammoinium chloride, 1:5 (molar ratio) is placed in nothing in proportion with sodium hydroxide
In alcoholic solvent, 40 DEG C of water-bath temperature control, it is stirred to react 10min, filters and steams solvent and obtain quaternary amine alkali benzyl triethyl ammonium hydrogen
Amine-oxides.Finally by the ethanol solution of 1% quaternary amine alkali benzyltriethylammonium hydroxide and 0.1% sodium hydrate aqueous solution 1:1
(mass ratio) compounding obtains chloride shift agent.
Embodiment 7:
Etoh solvent 500ml is weighed, the three-necked flask (1000ml) of blender, reflux condenser and thermometer is placed in
In, the successively benzyl chloride (126.58g) of additional proportion (molar ratio 1:1), triethylamine (101.19g), starting stirring makes reactant
It is sufficiently mixed, 45 DEG C of water-bath temperature control, reaction time 20min, generates benzyltriethylammoinium chloride, solvent is evaporated off, obtain white crystalline substance
Body benzyltriethylammoinium chloride.By quaternary ammonium salt benzyltriethylammoinium chloride, 1:10 (molar ratio) is placed in nothing in proportion with sodium hydroxide
In alcoholic solvent, 40 DEG C of water-bath temperature control, it is stirred to react 10min, filters and steams solvent and obtain quaternary amine alkali benzyl triethyl ammonium hydrogen
Amine-oxides.Finally by the ethanol solution of 1% quaternary amine alkali benzyltriethylammonium hydroxide and 0.1% sodium hydrate aqueous solution 1:1
(mass ratio) compounding obtains chloride shift agent.
Embodiment 8:
Etoh solvent 500ml is weighed, the three-necked flask (1000ml) of blender, reflux condenser and thermometer is placed in
In, the successively benzyl chloride (126.58g) of additional proportion (molar ratio 1:1), trimethylamine (59.11g), starting stirring fills reactant
Divide mixing, 10 DEG C of water-bath temperature control, reaction time 30min, generates benzyltrimethylammonium chloride, solvent is evaporated off, obtains white crystal
Benzyltrimethylammonium chloride.By quaternary ammonium salt benzyltrimethylammonium chloride and sodium hydroxide in proportion 1:1 (molar ratio) be placed in it is anhydrous
In alcohol solvent, 40 DEG C of water-bath temperature control, it is stirred to react 10min, filters and steams solvent and obtain quaternary amine alkali benzyl trimethyl hydrogen-oxygen
Change ammonium.Finally by the ethanol solution of 1% quaternary amine alkali benzyltrimethylammonium hydroxide and 0.1% sodium hydrate aqueous solution 1:5 (matter
Amount ratio) compounding obtain chloride shift agent.
Embodiment 9:
Etoh solvent 500ml is weighed, the three-necked flask (1000ml) of blender, reflux condenser and thermometer is placed in
In, the successively benzyl chloride (126.58g) of additional proportion (molar ratio 1:1), trimethylamine (59.11g), starting stirring fills reactant
Divide mixing, 10 DEG C of water-bath temperature control, reaction time 30min, generates benzyltrimethylammonium chloride, solvent is evaporated off, obtains white crystal
Benzyltrimethylammonium chloride.By quaternary ammonium salt benzyltrimethylammonium chloride and sodium hydroxide in proportion 1:1 (molar ratio) be placed in it is anhydrous
In alcohol solvent, 40 DEG C of water-bath temperature control, it is stirred to react 10min, filters and steams solvent and obtain quaternary amine alkali benzyl trimethyl hydrogen-oxygen
Change ammonium.Finally by the ethanol solution of 1% quaternary amine alkali benzyltrimethylammonium hydroxide and 0.1% sodium hydrate aqueous solution 1:10
(mass ratio) compounding obtains chloride shift agent.
Embodiment 10:
Etoh solvent 500ml is weighed, the three-necked flask (1000ml) of blender, reflux condenser and thermometer is placed in
In, the successively benzyl chloride (126.58g) of additional proportion (molar ratio 1:1), triethylamine (101.19g), starting stirring makes reactant
It is sufficiently mixed, 45 DEG C of water-bath temperature control, reaction time 20min, generates benzyltriethylammoinium chloride, solvent is evaporated off, obtain white crystalline substance
Body benzyltriethylammoinium chloride.By quaternary ammonium salt benzyltriethylammoinium chloride, 1:10 (molar ratio) is placed in nothing in proportion with sodium hydroxide
In alcoholic solvent, 70 DEG C of water-bath temperature control, it is stirred to react 20min, filters and steams solvent and obtain quaternary amine alkali benzyl triethyl ammonium hydrogen
Amine-oxides.Finally by the ethanol solution of 1% quaternary amine alkali benzyltriethylammonium hydroxide and 0.1% sodium hydrate aqueous solution 1:1
(mass ratio) compounding obtains chloride shift agent.
Embodiment 11:
Etoh solvent 500ml is weighed, the three-necked flask (1000ml) of blender, reflux condenser and thermometer is placed in
In, the successively benzyl chloride (126.58g) of additional proportion (molar ratio 1:1), tripropyl amine (TPA) (143.27g), starting stirring makes reactant
It is sufficiently mixed, 80 DEG C of water-bath temperature control, reaction time 10min, generates benzyl tripropyl ammonium chloride, solvent is evaporated off, obtain white crystalline substance
Body benzyl tripropyl ammonium chloride.By quaternary ammonium salt benzyl tripropyl ammonium chloride, 1:1 (molar ratio) is placed in nothing in proportion with sodium hydroxide
In alcoholic solvent, 100 DEG C of water-bath temperature control, it is stirred to react 30min, filters and steams solvent and obtain quaternary amine alkali benzyl tripropyl hydrogen
Amine-oxides.Finally by the ethanol solution and 0.1% sodium hydrate aqueous solution 1:1 of 1% quaternary amine alkali benzyl tripropyl ammonium hydroxide
(mass ratio) compounding obtains chloride shift agent.
Embodiment 12:
Etoh solvent 500ml is weighed, the three-necked flask (1000ml) of blender, reflux condenser and thermometer is placed in
In, the successively benzyl chloride (126.58g) of additional proportion (molar ratio 1:1), trimethylamine (59.11g), starting stirring fills reactant
Divide mixing, 10 DEG C of water-bath temperature control, reaction time 30min, generates benzyltrimethylammonium chloride, solvent is evaporated off, obtains white crystal
Benzyltrimethylammonium chloride.By quaternary ammonium salt benzyltrimethylammonium chloride and sodium hydroxide in proportion 1:1 (molar ratio) be placed in it is anhydrous
In alcohol solvent, 40 DEG C of water-bath temperature control, it is stirred to react 10min, filters and steams solvent and obtain quaternary amine alkali benzyl trimethyl hydrogen-oxygen
Change ammonium.Finally by the ethanol solution of 5.5% quaternary amine alkali benzyltrimethylammonium hydroxide and 5% sodium hydrate aqueous solution 1:5 (matter
Amount ratio) compounding obtain chloride shift agent.
Embodiment 13:
Etoh solvent 500ml is weighed, the three-necked flask (1000ml) of blender, reflux condenser and thermometer is placed in
In, the successively benzyl chloride (126.58g) of additional proportion (molar ratio 1:1), trimethylamine (59.11g), starting stirring fills reactant
Divide mixing, 10 DEG C of water-bath temperature control, reaction time 30min, generates benzyltrimethylammonium chloride, solvent is evaporated off, obtains white crystal
Benzyltrimethylammonium chloride.By quaternary ammonium salt benzyltrimethylammonium chloride and sodium hydroxide in proportion 1:1 (molar ratio) be placed in it is anhydrous
In alcohol solvent, 40 DEG C of water-bath temperature control, it is stirred to react 10min, filters and steams solvent and obtain quaternary amine alkali benzyl trimethyl hydrogen-oxygen
Change ammonium.Finally by the ethanol solution of 10% quaternary amine alkali benzyltrimethylammonium hydroxide and 10% sodium hydrate aqueous solution 1:5 (matter
Amount ratio) compounding obtain chloride shift agent.
Dechlorination evaluation experimental
De- preceding mixed crude 100L is taken from refinery decompressioning device.Using D. Lab PY-2C electro-desalting tester, fill
Divide washing removing butter, then dechlorination evaluation experimental is carried out to the chloride shift agent in embodiment 1-13.
In experiment electric desalting apparatus, mixed crude, chloride shift agent and distilled water are sequentially added, controls 110 DEG C of temperature, reaction
Time 0.5-1h.After reaction, grease layering is calculated in crude oil with the content of organochlorine in Microcoulomb instrument measurement oil reservoir with following formula
Organochlorine removes chlorine:
Wherein, T is organic dechlorination rate, m0It is content of organic chloride (μ gg in de- preceding crude oil-1), m1Have in crude oil after de-
Machine chlorinity (μ gg-1).Using the chloride shift agent in 101899321 A of patent CN in comparative test, 1 the results are shown in Table.
1 dechlorination effect of table
From table 1, it is apparent that the chloride shift agent of heretofore described method preparation can be by the organochlorine in crude oil
Removing well, average removal efficiency are up to 90%, the dechlorination effect of far superior to existing patent.
Claims (8)
1. a kind of preparation method of the chloride shift agent for electric desalting apparatus, it is characterised in that: by tertiary amine and benzyl chloride in solvent
Under the conditions of generate quaternary amine, quaternary amine and sodium hydroxide and generate quaternary amine alkali under the conditions of dehydrated alcohol, the ethyl alcohol of quaternary amine alkali is molten
Liquid is compounded with the aqueous solution of sodium hydroxide, obtains the chloride shift agent for electric desalting apparatus.
2. preparation method according to claim 1, it is characterised in that the tertiary amine includes trimethylamine, triethylamine, 3 third
One of amine, N- methyl-diethyl-amine.
3. preparation method according to claim 1, it is characterised in that the solvent is neutrality or micropolar, including second
One of alcohol, water, tetrahydrofuran.
4. preparation method according to claim 1, it is characterised in that generate the reaction condition of quaternary ammonium salt are as follows: temperature 10~80
DEG C, 10~30min of time.
5. preparation method according to claim 1, it is characterised in that the molar ratio of quaternary amine and sodium hydroxide 1:1~
10。
6. preparation method according to claim 1, it is characterised in that generate the reaction condition of quaternary amine alkali are as follows: temperature 40~
100 DEG C, 10~30min of time.
7. preparation method according to claim 1, it is characterised in that the ethanol solution mass percentage 1%- of quaternary amine alkali
10%.
8. preparation method according to claim 1, it is characterised in that the aqueous solution mass percentage 0.1- of sodium hydroxide
10%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113755204A (en) * | 2021-09-22 | 2021-12-07 | 中国石油大学(华东) | Crude oil organochlorine transfer agent and dechlorination method |
| CN116135955A (en) * | 2022-12-27 | 2023-05-19 | 宁波中循环保科技有限公司 | Method for removing chlorine in waste lubricating oil based on modified alkaline hydroxide |
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| CN102492458A (en) * | 2011-11-22 | 2012-06-13 | 沈阳工业大学 | Additive for removing organochlorine from crude oil and removal technology thereof |
| CN105368580A (en) * | 2014-08-25 | 2016-03-02 | 中石化洛阳工程有限公司 | Organic chloride removing method for waste cooking oil |
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- 2018-09-07 CN CN201811040628.9A patent/CN109439362A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492458A (en) * | 2011-11-22 | 2012-06-13 | 沈阳工业大学 | Additive for removing organochlorine from crude oil and removal technology thereof |
| CN105368580A (en) * | 2014-08-25 | 2016-03-02 | 中石化洛阳工程有限公司 | Organic chloride removing method for waste cooking oil |
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| 王鹤义等: "《有机化学》", 31 December 2006, 中国石油大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113755204A (en) * | 2021-09-22 | 2021-12-07 | 中国石油大学(华东) | Crude oil organochlorine transfer agent and dechlorination method |
| CN116135955A (en) * | 2022-12-27 | 2023-05-19 | 宁波中循环保科技有限公司 | Method for removing chlorine in waste lubricating oil based on modified alkaline hydroxide |
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Application publication date: 20190308 |