Recycling method of hydrocarbon oil metal-removing agent

A demetallizing agent and hydrocarbon oil technology, which is applied in the refining of hydrocarbon oil, petroleum industry, and multi-stage series refining process treatment, etc., can solve the problems of short service life of resin, limited removal rate, serious environmental pollution, etc. Achieve high efficiency, strong practicability and environmental friendliness

Active Publication Date: 2012-04-04
PETROCHINA CO LTD
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Problems solved by technology

如CN86107286、CN1036981、CN1267707、CN87105863、CN1054261、CN1055552、CN107673、CN110575、CN221017、CN1221018、CN1245201、CN1693424、CN1657596、CN1431277、CN1454967、CN1982413、CN101085932、CN101067012等均公开的是上述脱金属剂和(或)脱 Hydrocarbon oil demetallization process for one-time use of metal auxiliary agents. This process has the advantages of effective removal of hydrocarbon oil and easy operation, but it has serious environmental pollution. Demetallization agent and / or demetallization auxiliary agent , demulsifier and waste of water resources, as well as the resulting defects of high processing cost per ton of hydrocarbon oil
CN1454969 discloses a hydrocarbon oil demetallization circulation method, which solves the above problems well, but there is incomplete solid-liquid separation, and the unremoved insoluble or water-insoluble metal salt slag enters with the recycled aqueous solution. The electric desalination system affects the normal operation of the electric desalination and subsequent devices, and there are defects such as excessive use of precipitant, which causes corrosion of the device
WO98 / 14534 announced a resin decalcification process, which is to make the resin into a bed to let the crude oil pass through or suspend the resin in the crude oil, and transfer the calcium in the crude oil into the resin. After the reaction, the crude oil and the resin can be separated to obtain For decalcified crude oil, the used resin can be regenerated after acid treatment, but there are problems such as high decalcification cost, limited removal rate of tightly bound organic calcium, poor applicability, short service life of resin, and difficulty in engineering

Method used

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  • Recycling method of hydrocarbon oil metal-removing agent
  • Recycling method of hydrocarbon oil metal-removing agent
  • Recycling method of hydrocarbon oil metal-removing agent

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Hydrocarbon oil demetallizer: 10% demetallizer + 90% demulsifier;

[0028] Ordinary third-line distillate oil: calcium 41.3mg / L, magnesium 2.98mg / L, sodium 18.8mg / L, vanadium 13.1mg / L, sulfur 1310mg / L;

[0029]Mix 0.002% of the hydrocarbon oil demetallizing agent and 5% water with the normal three-line distillate oil at 100°C with a static mixer at a mixing pressure difference of 0.5MPa for 2 minutes to control the diameter of the oil-water particles at Within the range of 0.1 μm to 50 μm, put it in an electric desalting tank, and act for 20 / 10 minutes under the conditions of desalination temperature of 100°C and strong and weak electric fields of 1500 / 100v / cm respectively. After oil and water are separated, analyze the calcium content / decalcification rate of the purified oil 2.0mg / L / 95.2%, magnesium content / magnesium removal rate 0.189mg / L / 93.7%, sodium content 0.7mg / L / 96.3%, vanadium content / vanadium removal rate 0.41mg / L / 96.9%, sulfur The content is 1300mg / L. The i...

Embodiment 2

[0038] Hydrocarbon oil demetallizer: 50% demetallizer + 50% demulsifier;

[0039] Crude oil: calcium 265mg / L, magnesium 1.54mg / L, sodium 5.8mg / L, vanadium 2.6mg / L, iron 7.6mg / L;

[0040] Mix 0.8% of crude oil with hydrocarbon oil demetallizer, 10% of water and crude oil with a stirrer at 60°C and 0.1MPa for 30 minutes, put them in an electric desalting tank, desalting temperature at 50°C, and strong and weak electric fields are respectively 1000 / 500v / cm for 60 / 20min, after oil-water separation, analysis of calcium content / decalcification rate in the purified oil was 27.8mg / L / 89.5%, magnesium content / magnesium removal rate was 0.412mg / L / 73.2%, sodium content 3.3mg / L / 43.1%, vanadium content / removal rate 0.342mg / L / 86.8%, iron content 5.60mg / L / 26.3%. The isolated desalted aqueous solution containing metal salts adopts the GB7476-87 test method (determination of calcium content in water by EDTA titration method) to measure that the calcium content in water is 0.35%. After the desa...

Embodiment 3

[0050] Hydrocarbon oil demetallizer: 99.5% demetallizer + 0% demulsifier + 0.5% water

[0051] Crude oil: calcium 680mg / L, magnesium 5.02mg / L, iron 20.6mg / L, sodium 45mg / L, vanadium 3.10mg / L

[0052] Cut the hydrocarbon oil demetallizing agent accounting for 2% of crude oil, 20% of water and crude oil with a shearing instrument at a temperature of 50°C and a pressure of 0.5Mpa until the diameter of the oil-water particles is within the range of 0.1 μm to 50 μm, and set In the electric desalting tank, the desalination temperature is 150°C, and the strong and weak electric fields are 500 / 50v / cm respectively, and the action is 200 / 60min. After the oil and water are separated, the calcium content in the purified oil is analyzed / the decalcification rate is 45.0mg / L / 93.4%. Magnesium content / magnesium removal rate is 0.61mg / L / 87.8%, sodium content is 2.3mg / L / 94.9%, vanadium content / vanadium removal rate is 0.25mg / L / 91.9%, iron content is 5.1mg / L / 75.2% . The isolated desalted aqueou...

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Abstract

The invention relates to a recycling method of a hydrocarbon oil metal-removing agent. According to the invention, the hydrocarbon oil metal-removing agent is sufficiently mixed with hydrocarbon oil, and the mixture is processed through a common electrostatic desalting process, such that metal-ion-removed hydrocarbon oil is obtained; a desalting solution containing the metal ions is filtered, and is subject to ion exchange with ion exchange resin filled in a double-layered bed ion exchanger, such that a recycled water solution containing the hydrocarbon oil metal-removing agent is obtained; the recycled water solution containing the hydrocarbon oil metal-removing agent is well mixed with hydrocarbon oil and is reused; the failed ion exchange resin is processed through a regeneration treatment, and is repeatedly used. In prior arts, solid-liquid separation is not sufficiently carried out, part of metal salt slag which is not easily soluble or insoluble in water enters the electrostatic desalting system along with the circulated water solution, such that normal operation of the apparatus is influenced; also, a precipitant is over-dosed, such that apparatus corrosion is caused. With the method provided by the invention, the defects are overcome. The method is advantaged in environment friendliness and high metal removing rate.

Description

technical field [0001] The invention relates to a recycling method of a metal removal agent for removing metal from hydrocarbon oil. Background technique [0002] As the oilfield enters the middle and late stages of exploitation, the exploitation of a large amount of heavy oil or the remaining oil of primary and secondary oil recovery, due to the use of chemical recovery aids and other tertiary oil recovery technologies, causes the types and contents of metal ions in crude oil, such as calcium, magnesium, iron, nickel, Vanadium, etc. increased greatly, and showed a rising trend. The harm caused by the existence of the above-mentioned metal ions to crude oil distillation and secondary processing has attracted the attention of people in the industry as early as the 1980s, and technologies for removing metal ions in different ways from hydrocarbon oil have been developed successively. . Among them, the research on the demetallization technology combining the demetallization t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G53/02C10G29/20C10G29/22
Inventor 马忠庭牛春革张海兵于曙艳韩云乔文马玲
Owner PETROCHINA CO LTD
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