CN104059689A - Oil product dechlorination method - Google Patents
Oil product dechlorination method Download PDFInfo
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- CN104059689A CN104059689A CN201410291700.0A CN201410291700A CN104059689A CN 104059689 A CN104059689 A CN 104059689A CN 201410291700 A CN201410291700 A CN 201410291700A CN 104059689 A CN104059689 A CN 104059689A
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- dechlorination
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Abstract
The invention relates to an oil product dechlorination method which comprises the following steps: adding alkaline matter and salt into deionized water to prepare an alkaline salt solution of which the concentration of the compound disclosed in the specification is 4-6.5 mol/L and the anionic concentration of salt is 1-1.5 mol/L; mixing the alkaline salt solution and the oil product according to the mole ratio of the sum of the compound disclosed in the specification and salt anions to the compound disclosed in the specification of (15.5-5000):1; and reacting under reflux for 2-4 hours, cooling, standing, and skimming to obtain the dechlorinated oil product, wherein the alkaline matter is alkali-metal hydroxide, and the salt is nitrate or phosphate of alkali metal and alkali earth metal. The method has the characteristics of mild technological conditions, favorable dechlorination effect and the like, is simple to operate, and is suitable for carrying out dechlorination pretreatment on low-chlorine-content and high-chlorine-content oil products and industrial waste oil.
Description
Technical field
The present invention relates to a kind of oil product dechlorination method, belong to refining of petroleum field.
Background technology
In recent years, many oil fields are in order to increase output, in the technique such as oil production and processing, add multiple auxiliary agent to increase oil offtake, cause content of organic chloride in the distillate of crude oil and crude oil processing significantly to improve, and utilize in the various industrial waste oils of oil fuel that waste tyre pyrolytic produces and recovery and also contain a large amount of organic chlorides.
Muriate in above-mentioned oil product, in the process of processing, can bring very large harm: 1, poisoning of catalyst.In the course of processing of oil product, the inorganic chlorine of organic chloride deposits yields can cause poisoning of catalyst; 2, pipeline obstruction.In the process of shortening, organic chloride can produce HCl, and the material that contains N may produce NH
3, cause NH
3with HCl in conjunction with generate NH
4cl, causes pipeline obstruction; 3, equipment corrosion.Once the HCl producing in shortening process runs into water vapour, will produce strong corrodibility, very harmful to equipment.Therefore, need to control the cl content in oil product.Along with the development of oil Refining Technologies, require also higher to the saltiness after crude oil desalting.The specific requirement of current domestic crude oil is: pre-protection against corrosion, and after crude oil desalting, saltiness can not be greater than 5 mg/L; Prevent poisoning of catalyst, after crude oil desalting, saltiness can not be greater than 3 mg/L.
The kinds of processes methods such as the adsorbing and removing method that mainly contains, phase-transfer catalyst removal method, hydrogenation and removing method that remove of organochlorine.Hydrogenation and removing technical maturity, but need more complicated equipment and higher running cost; Although solid adsorbent has higher adsorbing and removing rate, but due to the restriction of its loading capacity, in the time that chloride content is higher, sorbent material can need manipulation of regeneration because of the quick minimizing of loading capacity, regeneration certainly will increase the difficulty of this technological operation frequently, increases cost; Phase-transfer catalyst in reaction process can with water in ionic bond, and utilize self affinity to organic solvent, in organic phase, impel reaction to occur the reactant transfer in water, effectively raise dechlorination rate, but phase-transfer catalyst phase price is higher.
Summary of the invention
The present invention has proposed to the deficiencies in the prior art part the oil product dechlorination method that a kind of processing condition are very gentle, dechlorination method is simple, cost is low, reaction efficiency is high, easy to operate, significant for low chlorine and high cl content oil product pre-treatment dechlorination.
A kind of oil product dechlorination method provided by the invention, adds alkaline matter and salt in deionized water, makes
concentration is that the anion concentration of 4～6.5 mol/L, salt is the alkaline salt solution of 1～1.5 mol/L, and this alkaline salt solution and oil product are pressed
with the negatively charged ion mole number sum of salt with
the ratio of mole number be (15.5～5000): 1 mixes, and at 100 DEG C～180 DEG C, back flow reaction 2～4 h, obtain the oil product after dechlorination through cooling, standing, separatory;
Described alkaline matter is alkali-metal oxyhydroxide; Described salt is nitrate or the phosphoric acid salt of alkali and alkaline earth metal ions.
Described oil product is crude oil, waste tyre pyrolytic oil, industrial waste oil or petroleum naphtha.
Described alkaline matter is preferably sodium hydroxide or potassium hydroxide.
Described salt is preferably SODIUMNITRATE, saltpetre, sodium phosphate or potassiumphosphate.
The invention has the advantages that alkali-metal alkaline matter and salt formation alkaline salt solution soluble in water, alkaline matter
with nitrate, phosphatic
,
can serve as nucleophilic reagent, can be effectively under the condition of heating and organic chloride generation nucleophilic substitution reaction, thus realize the dechlorination effect of organic chloride.The present invention passes through
with
,
nucleophilic character, effectively improved the effect of dechlorination, and cost is lower, easy to operate, processing condition gentleness, significant for low chlorine and high cl content oil product dechlorination pre-treatment.
Embodiment
Embodiment mono-:
By 0.369mol NaOH and 0.08mol K
3pO
4mix, stir and be dissolved in the deionized water of 60 mL, after dissolving completely, add 60 mL waste tyre pyrolytic oil, wherein the chloride content in 60 mL waste tyre pyrolytic oil is 21.6 mmol.After mixing, pour in three-necked flask, reflux 4 h at 100 DEG C, after reaction finishes, question response liquid cooling but, moves to separating funnel and leaves standstill 1 h, obtains upper strata oil sample, and after mensuration dechlorination, the chloride content of oil sample is 9.96 mmol, and dechlorination rate is 53.85%.
Embodiment bis-:
By 0.184mol NaOH and 0.04mol KNO
3mix, stir and be dissolved in the deionized water of 30 ml, the automobile gear oil that adds 30 mL to reclaim after dissolving completely, wherein the chloride content in 30 mL gear oils is 0.036 mmol.After mixing, pour in three-necked flask, reflux 4 h at 120 DEG C, after reaction finishes, question response liquid cooling but, moves to separating funnel and leaves standstill 1 h, obtains upper strata oil sample, and after mensuration dechlorination, in oil sample, chloride content is 0.0049 mmol, and dechlorination rate reaches 86.26%.
Embodiment tri-:
By 0.225mol KOH and 0.06mol NaNO
3mix, stir and be dissolved in 45 mL deionized waters, after dissolving completely, add 30 mL waste tyre pyrolytic oil, wherein the chloride content in 30 mL waste tyre pyrolytic oil is 10.8 mmol.After mixing, pour in three-necked flask, reflux 4 h at 140 DEG C, after reaction finishes, question response liquid cooling but, moves to separating funnel and leaves standstill 1 h, obtains upper strata oil sample, and after mensuration dechlorination, in oil sample, chloride content is 2.966 mmol, and dechlorination rate is 72.53%.
Embodiment tetra-:
By 0.18mol KOH and 0.04mol K
3pO
4mix, stir and be dissolved in 30 mL deionized waters, after dissolving completely, add 30 mL oil from Shengli oil fields, wherein the chloride content in 30 mL oil from Shengli oil fields is 0.049 mmol.After mixing, pour in three-necked flask, reflux 4 h at 160 DEG C, after reaction finishes, question response liquid cooling but, moves to separating funnel and leaves standstill 1 h, obtains upper strata oil sample, and after mensuration dechlorination, oil sample chloride content is 0.0025 mmol, and dechlorination rate is 94.80%.
Embodiment five:
By 0.184mol NaOH and 0.04mol KNO
3mix, stir and be dissolved in the deionized water of 30 ml, after dissolving completely, add 30 mL petroleum naphthas, wherein the chloride content in 30 mL petroleum naphthas is 0.08 mmol.After mixing, pour in three-necked flask, reflux 4 h at 180 DEG C, after reaction finishes, question response liquid cooling but, moves to separating funnel and leaves standstill 1 h, obtains upper strata oil sample, and after mensuration dechlorination, oil sample chloride content is 0.00388 mmol, and dechlorination rate reaches 95.15%.
Claims (4)
1. an oil product dechlorination method, is characterized in that, alkaline matter and salt are added in deionized water, makes
concentration is that the anion concentration of 4～6.5 mol/L, salt is the alkaline salt solution of 1～1.5 mol/L, and this alkaline salt solution and oil product are pressed
with the negatively charged ion mole number sum of salt with
the ratio of mole number be (15.5～5000): 1 mixes, and at 100 DEG C～180 DEG C, back flow reaction 2～4 h, obtain the oil product after dechlorination through cooling, standing, separatory;
Described alkaline matter is alkali-metal oxyhydroxide; Described salt is nitrate or the phosphoric acid salt of alkali and alkaline earth metal ions.
2. a kind of oil product dechlorination method according to claim 1, is characterized in that, described oil product is crude oil, waste tyre pyrolytic oil, industrial waste oil or petroleum naphtha.
3. a kind of oil product dechlorination method according to claim 1, is characterized in that, alkaline matter is sodium hydroxide or potassium hydroxide.
4. a kind of oil product dechlorination method according to claim 1, is characterized in that, described salt is SODIUMNITRATE, saltpetre, sodium phosphate or potassiumphosphate.
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| CN201410291700.0A CN104059689B (en) | 2014-06-26 | 2014-06-26 | A kind of oil product dechlorination method |
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|---|---|---|---|
| CN201410291700.0A CN104059689B (en) | 2014-06-26 | 2014-06-26 | A kind of oil product dechlorination method |
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| CN104059689A true CN104059689A (en) | 2014-09-24 |
| CN104059689B CN104059689B (en) | 2016-01-13 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104726134A (en) * | 2015-03-18 | 2015-06-24 | 大连理工大学 | Method for producing high-quality gasoline/diesel from chlorine-containing plastic oil |
| CN111019750A (en) * | 2019-12-23 | 2020-04-17 | 宁波中循环保科技有限公司 | Method for removing chlorine in waste engine oil by using strong-alkaline ionic liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100147746A1 (en) * | 2008-12-16 | 2010-06-17 | Chevron U.S.A. Inc | Reduction of organic halide contamination in hydrocarbon products |
| WO2012038413A1 (en) * | 2010-09-23 | 2012-03-29 | Shell Internationale Research Maatschappij B.V. | Process for reducing the halogen content of a hydrocarbon product stream by mixing with an aqeous caustic solution in the presence of a phase transfer catalyst |
-
2014
- 2014-06-26 CN CN201410291700.0A patent/CN104059689B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100147746A1 (en) * | 2008-12-16 | 2010-06-17 | Chevron U.S.A. Inc | Reduction of organic halide contamination in hydrocarbon products |
| CN102282111A (en) * | 2008-12-16 | 2011-12-14 | 雪佛龙美国公司 | Reduction of organic halide contamination in hydrocarbon products |
| WO2012038413A1 (en) * | 2010-09-23 | 2012-03-29 | Shell Internationale Research Maatschappij B.V. | Process for reducing the halogen content of a hydrocarbon product stream by mixing with an aqeous caustic solution in the presence of a phase transfer catalyst |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104726134A (en) * | 2015-03-18 | 2015-06-24 | 大连理工大学 | Method for producing high-quality gasoline/diesel from chlorine-containing plastic oil |
| CN104726134B (en) * | 2015-03-18 | 2017-05-03 | 大连理工大学 | Method for producing high-quality gasoline/diesel from chlorine-containing plastic oil |
| CN111019750A (en) * | 2019-12-23 | 2020-04-17 | 宁波中循环保科技有限公司 | Method for removing chlorine in waste engine oil by using strong-alkaline ionic liquid |
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| CN104059689B (en) | 2016-01-13 |
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