CN109082295B - Coke inhibiting liquid yield increasing agent and preparation method thereof - Google Patents
Coke inhibiting liquid yield increasing agent and preparation method thereof Download PDFInfo
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- CN109082295B CN109082295B CN201811019475.XA CN201811019475A CN109082295B CN 109082295 B CN109082295 B CN 109082295B CN 201811019475 A CN201811019475 A CN 201811019475A CN 109082295 B CN109082295 B CN 109082295B
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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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
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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
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
-
- 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
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/02—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of corrosion inhibitors
-
- 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
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
The invention relates to a coke inhibiting liquid yield increasing agent and a preparation method thereof, wherein the coke inhibiting liquid yield increasing agent adopts an antioxidant, a scale inhibitor, a polymerization inhibitor, a dispersant, a corrosion inhibitor and solvent oil as raw materials and is prepared in a proper weight ratio, under the synergistic effect of the raw material components, the finally prepared coke inhibiting liquid yield increasing agent inhibits the process from coking, reduces the gas yield, increases the liquid oil yield, and has the advantages of simple operation and good economic benefit.
Description
Technical Field
The invention belongs to the technical field of oil refining auxiliaries, and particularly relates to a coke inhibiting liquid yield increasing agent and a preparation method thereof.
Background
At present, more than 85% of coking processes in the world belong to the delayed coking type. In the process, the heavy oil is heated to the temperature (480-550 ℃) required by coking reaction through a tubular heating furnace, and is rapidly separated from the heating furnace tube, and the oil is subjected to cracking and condensation reaction in a coke tower to generate a gas product, a liquid product with different boiling points and a coke product. The process has mature technology and low operation cost, is suitable for deep processing of heavy oil with various properties, and is particularly suitable for treating a large amount of inferior residual oil.
The main goals of delayed coker operation and design are to maximize liquid yield, reduce coke production, and produce gasoline and diesel suitable for downstream unit processing. Generally, the liquid yield of the delayed coking unit is about 70 percent, and the coke value is low, so that various large petroleum companies in the world continuously research and improve the delayed coking technology to improve the liquid yield and reduce the coke yield, and the liquid yield can bring huge economic benefits to refineries every 1 percent. Therefore, the coke inhibiting and liquid increasing agent is applied to the delayed coking device, so that the liquid yield is improved, and the method has important practical significance.
In China, a plurality of researches on the aspect of delayed coking liquid increasing agent are carried out in the year. The patent CN1244669C discloses a heavy oil delayed coking cracking activating additive and a preparation method thereof, and provides the heavy oil delayed coking cracking activating additive, which comprises 20-40 wt% of lanthanide rare earth organic compound (lanthanum, praseodymium or cerium salt of naphthenic acid or fatty acid), 5-15 wt% of metal passivator (one of dialkyl molybdenum dithiophosphate, dialkyl antimony dithiophosphate or dialkyl tin dithiophosphate) and polymer surfactant (C)8-C12One of alkylphenol polyoxyethylene ether and sorbitan polyoxyethylene) 10-30 wt%, and solvent (No. 120 solvent oil or diesel oil or kerosene) 10-30 wt%. However, the above-mentioned techniquesThe prepared delayed coking liquid increasing agent has the advantages of general coke inhibiting and liquid increasing performance of products, large dosage, high cost and poor effect when in use.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a coke inhibiting liquid yield increasing agent capable of effectively inhibiting coke yield and increasing light oil liquid yield and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a coke inhibiting liquid yield increasing agent comprises the following raw material components:
2-5 parts of antioxidant;
5-10 parts of scale inhibitor;
5-8 parts of polymerization inhibitor;
10-20 parts of a dispersant;
5-10 parts of corrosion inhibitor;
47-73 parts of solvent oil.
Further preferably, the raw material components of the coke inhibiting liquid yield increasing agent comprise:
3-4 parts of antioxidant;
7-8 parts of scale inhibitor;
6-7 parts of polymerization inhibitor;
12-18 parts of a dispersant;
7-8 parts of corrosion inhibitor;
55-65 parts of solvent oil.
Further preferably, the raw material components of the coke inhibiting liquid yield increasing agent comprise:
3.5 parts by weight of antioxidant;
7.5 parts of scale inhibitor;
6.5 parts of polymerization inhibitor;
15 parts of a dispersant;
7.5 parts of corrosion inhibitor;
60 parts of solvent oil.
The antioxidant is a mixture of N, N '-di-sec-butyl-p-phenylenediamine, alkylated diphenylamine and N, N' -bis-salicylidene propane diamine in a mass ratio of 2-4:1-2: 1-2.
The scale inhibitor is a mixture of polymaleic anhydride and dodecyl amine polyoxyethylene ether according to the mass ratio of 1:4-4: 1.
The polymerization inhibitor is a mixture of p-tert-butyl catechol and o-tert-butyl 4, 6-dinitrophenol according to the mass ratio of 1:2-2: 1.
The dispersing agent is propylene glycol block polyether.
The corrosion inhibitor is oleic hydroxyethyl imidazoline.
The solvent oil is a mixture of 12# solvent oil and 20# solvent oil according to the mass ratio of 1:2-2: 1.
The preparation method of the coke inhibiting liquid yield increasing agent comprises the following steps:
respectively taking the antioxidant, the scale inhibitor, the polymerization inhibitor, the dispersant, the corrosion inhibitor and the solvent oil, and stirring and mixing for 20-30min under the conditions of normal temperature and normal pressure to obtain the catalyst.
The invention has the beneficial effects that:
the coke inhibiting liquid yield increasing agent provided by the invention adopts an antioxidant, a scale inhibitor, a polymerization inhibitor, a dispersant, a corrosion inhibitor and solvent oil as raw materials, is prepared in a proper weight ratio, and is finally prepared under the synergistic effect of the raw material components, so that the coke inhibiting liquid yield increasing agent can inhibit the process coking, reduce the gas yield and increase the liquid oil yield on the premise of not influencing the product property, and is simple to operate and good in economic benefit.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
In the following examples 1g is represented by 1 part by weight.
Example 1
The embodiment provides a coke inhibiting liquid yield increasing agent, which comprises the following raw material components:
2 parts of N, N' -di-sec-butyl-p-phenylenediamine;
10 parts of scale inhibitor polymaleic anhydride;
5 parts of p-tert-butyl catechol;
20 parts by weight of propylene glycol block polyether;
5 parts by weight of oleic acid base hydroxyethyl imidazoline;
20# solvent oil, 73 parts by weight.
Further, the embodiment provides a preparation method of the coke inhibiting liquid yield increasing agent, which includes the following steps:
respectively taking the antioxidant, the scale inhibitor, the polymerization inhibitor, the dispersant, the corrosion inhibitor and the solvent oil, and stirring and mixing for 20min under the conditions of normal temperature and normal pressure to obtain the catalyst.
Example 2
The embodiment provides a coke inhibiting liquid yield increasing agent, which comprises the following raw material components:
5 parts by weight of a mixture of N, N '-di-sec-butyl-p-phenylenediamine, alkylated diphenylamine and N, N' -bis-salicylidene propane diamine in a mass ratio of 4:2: 2;
5 parts of scale inhibitor;
8 parts of p-tert-butyl catechol;
10 parts by weight of propylene glycol block polyether;
10 parts by weight of oleic acid base hydroxyethyl imidazoline;
47 parts by weight of a mixture of No. 12 solvent oil and No. 20 solvent oil according to the mass ratio of 2: 1.
Further, the embodiment provides a preparation method of the coke inhibiting liquid yield increasing agent, which includes the following steps:
respectively taking the antioxidant, the scale inhibitor, the polymerization inhibitor, the dispersant, the corrosion inhibitor and the solvent oil, and stirring and mixing for 30min under the conditions of normal temperature and normal pressure to obtain the catalyst.
Example 3
The embodiment provides a coke inhibiting liquid yield increasing agent, which comprises the following raw material components:
3 parts by weight of a mixture consisting of N, N '-di-sec-butyl-p-phenylenediamine, alkylated diphenylamine and N, N' -bis-salicylidene propane diamine according to a mass ratio of 4:1: 2;
8 parts of a mixture of scale inhibitor polymaleic anhydride and dodecyl amine polyoxyethylene ether in a mass ratio of 1: 2;
6 parts by weight of a mixture of p-tert-butyl catechol and o-tert-butyl 4, 6-dinitrophenol in a mass ratio of 1: 1;
propylene glycol block polyether, 18 parts by weight;
oleic acid base hydroxyethyl imidazoline, 7 weight portions;
65 parts by weight of a mixture consisting of 12# solvent oil and 20# solvent oil according to a mass ratio of 1: 1.
Further, the embodiment provides a preparation method of the coke inhibiting liquid yield increasing agent, which includes the following steps:
respectively taking the antioxidant, the scale inhibitor, the polymerization inhibitor, the dispersant, the corrosion inhibitor and the solvent oil, and stirring and mixing for 25min under the conditions of normal temperature and normal pressure to obtain the catalyst.
Example 4
The embodiment provides a coke inhibiting liquid yield increasing agent, which comprises the following raw material components:
4 parts by weight of a mixture consisting of N, N '-di-sec-butyl-p-phenylenediamine, alkylated diphenylamine and N, N' -bis-salicylidene propane diamine according to the mass ratio of 2:2: 1;
7 parts by weight of a mixture of scale inhibitor polymaleic anhydride and dodecylamine polyoxyethylene ether according to the mass ratio of 2: 1;
7 parts by weight of a mixture of p-tert-butyl catechol and o-tert-butyl 4, 6-dinitrophenol in a mass ratio of 1: 1;
propylene glycol block polyether, 12 parts by weight;
oleic acid base hydroxyethyl imidazoline, 8 weight portions;
55 parts by weight of a mixture consisting of 12# solvent oil and 20# solvent oil according to the mass ratio of 1: 1.
Further, the embodiment provides a preparation method of the coke inhibiting liquid yield increasing agent, which includes the following steps:
respectively taking the antioxidant, the scale inhibitor, the polymerization inhibitor, the dispersant, the corrosion inhibitor and the solvent oil, and stirring and mixing for 22min under the conditions of normal temperature and normal pressure to obtain the catalyst.
Example 5
The embodiment provides a coke inhibiting liquid yield increasing agent, which comprises the following raw material components:
3.5 parts by weight of a mixture consisting of N, N '-di-sec-butyl-p-phenylenediamine, alkylated diphenylamine and N, N' -bis-salicylidene propylenediamine according to the mass ratio of 3:1.5: 1.5;
7.5 parts by weight of a mixture of scale inhibitor polymaleic anhydride and dodecylamine polyoxyethylene ether according to the mass ratio of 1: 1;
6.5 parts by weight of a mixture of p-tert-butyl catechol and o-tert-butyl 4, 6-dinitrophenol in a mass ratio of 1: 1;
15 parts by weight of propylene glycol block polyether;
oleic acid base hydroxyethyl imidazoline, 7.5 weight portions;
60 parts by weight of a mixture of 12# solvent oil and 20# solvent oil in a mass ratio of 1: 1.
Further, the embodiment provides a preparation method of the coke inhibiting liquid yield increasing agent, which includes the following steps:
respectively taking the antioxidant, the scale inhibitor, the polymerization inhibitor, the dispersant, the corrosion inhibitor and the solvent oil, and stirring and mixing for 25min under the conditions of normal temperature and normal pressure to obtain the catalyst.
Examples of the experiments
1. Evaluation of scorch retarding Effect
(1) Test procedure
Raw oil (vacuum residue) and the coke inhibiting liquid yield increasing agent obtained in examples 1-5 are added into an autoclave, the mixture is stirred for a plurality of hours at a certain temperature under the protection of nitrogen, a certain amount of raw oil is weighed after the experiment is finished, naphtha is used for diluting, a filter membrane is used for filtering, and the coke content in the solution is measured. The coke amount obtained after filtration was compared with the coke amount obtained by filtration of the raw oil without the addition of the coke inhibiting liquid yield increasing agent under the same conditions (blank test), and the coke inhibition ratio was calculated.
(2) Raw oil for test: the basic properties of a certain refinery vacuum residue are shown in table 1.
TABLE 1 basic Properties of vacuum residua
| Analysis item | Vacuum residuum of a refinery |
| Density, g/m3 | 982.4 |
| Viscosity (100 ℃ C.), mm2/s | 614.7 |
| Residual carbon content% | 16.34 |
| Sulfur content% | 12510 |
| Freezing point, DEG C | 37 |
| Total nitrogen, ppm | 6371 |
| Saturated hydrocarbon,% of | 21.65 |
| Aromatic hydrocarbons, based on | 37.96 |
| Pectin, is% | 38.27 |
| Asphaltene,% of | 2.12 |
Test temperature: 500 plus or minus 5 ℃; test time: about 6 hours;
the dosage of residual oil: about 1L; the adding amount of the medicament: 150 mg/L;
(3) the formula for calculating the coke resistance is as follows: specific coke rate (m)Air conditioner-mResistance device)/mAir conditionerX 100% where mAir conditioner、mResistance deviceThe coke amount of the blank test and the coke inhibiting liquid yield increasing agent test are respectively.
The results are shown in Table 2.
TABLE 2 results of the measurement of the scorch retarding rate of different samples
As can be seen from the data in Table 2, the addition of the coke inhibiting liquid yield increasing agent can obviously reduce the coke formation amount, the coke inhibiting performance of the coke inhibiting liquid yield increasing agent obtained in example 5 is optimal, and the increase value of the carbon residue in the oil sample is reduced most obviously after the test.
2. Evaluation of liquid yield
(1) Test procedure
In a simulated delayed coking device, the coke inhibiting liquid yield increasing agent obtained in the examples 1-5 is respectively added into a coking raw material, the coking raw material enters a coking tower through a heating furnace to carry out cracking reaction, and after the reaction product enters a fractionating tower to be separated, the reaction product can be generally separated into C4The following fraction, C5A 180 ℃ gasoline fraction, a 180 ℃ 350 ℃ diesel fraction, a 350 ℃ 450 ℃ wax oil fraction and a tail oil above 450 ℃. The coke produced by the reaction in the coke drum is deposited at the bottom of the drum, and when the coke drum is full, the feed can be stopped and the coke drum switched to another coke drum for the same operation. No coke inhibiting liquid yield increasing agent was added as a blank control.
(2) Test Process conditions
The feeding amount of the coking device is 0.5-1 kg/h;
outlet temperature of heating section of heating furnace: 480-520 ℃, and controlling the precision to +/-1 ℃;
the coke tower, the fractionating tower and the receiving tank respectively have the use pressures of 0.14-1Mpa, 0.14-0.8Mpa and 0.1-0.8Mpa, and the control precision is +/-5 ℃;
water injection amount: 20-100 ml/h;
the test results are shown in Table 3.
TABLE 3 liquid yield test results for different coke inhibiting liquid yield increasing agents
As can be seen from the data in Table 4, the addition of the coke inhibiting liquid yield increasing agent of the present invention during the delayed coking process can significantly reduce the yield of gas and coke, thereby improving the liquid yield. Meanwhile, after the chemical component analysis is carried out on the liquid product, the physical and chemical properties such as hydrocarbon composition, sulfur and nitrogen content, freezing point, carbon residue and the like of the gasoline fraction, the diesel oil fraction and the wax oil fraction before and after the coke inhibiting liquid yield increasing agent is added are not changed.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (3)
1. The coke inhibiting liquid yield increasing agent is characterized by comprising the following raw material components:
2-5 parts of antioxidant; the antioxidant is a mixture of N, N '-di-sec-butyl-p-phenylenediamine, alkylated diphenylamine and N, N' -bis-salicylidene propane diamine in a mass ratio of 2-4:1-2: 1-2;
5-10 parts of scale inhibitor; the scale inhibitor is a mixture of polymaleic anhydride and dodecyl amine polyoxyethylene ether according to the mass ratio of 1:4-4: 1;
5-8 parts of polymerization inhibitor; the polymerization inhibitor is a mixture of p-tert-butyl catechol and o-tert-butyl 4, 6-dinitrophenol according to the mass ratio of 1:2-2: 1;
10-20 parts of a dispersant; the dispersing agent is propylene glycol block polyether;
5-10 parts of corrosion inhibitor; the corrosion inhibitor is oleic hydroxyethyl imidazoline;
47-73 parts of solvent oil; the solvent oil is a mixture of 12# solvent oil and 20# solvent oil according to the mass ratio of 1:2-2: 1;
the preparation method of the coke inhibiting liquid yield increasing agent comprises the following steps:
respectively taking the antioxidant, the scale inhibitor, the polymerization inhibitor, the dispersant, the corrosion inhibitor and the solvent oil, and stirring and mixing for 20-30min under the conditions of normal temperature and normal pressure to obtain the catalyst.
2. The coke inhibiting liquid yield increasing agent of claim 1, wherein the raw material components comprise:
3-4 parts of antioxidant;
7-8 parts of scale inhibitor;
6-7 parts of polymerization inhibitor;
12-18 parts of a dispersant;
7-8 parts of corrosion inhibitor;
55-65 parts of solvent oil.
3. The coke inhibiting liquid yield increasing agent of claim 1, wherein the raw material components comprise:
3.5 parts by weight of antioxidant;
7.5 parts of scale inhibitor;
6.5 parts of polymerization inhibitor;
15 parts of a dispersant;
7.5 parts of corrosion inhibitor;
60 parts of solvent oil.
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| CN101665287A (en) * | 2008-09-05 | 2010-03-10 | 华东电力试验研究院有限公司 | Scale inhibitor |
| CN104479729A (en) * | 2014-10-31 | 2015-04-01 | 中国海洋石油总公司 | Coke inhibiting liquid yield increasing agent for refinery coking delaying apparatus, and preparation method thereof |
| CN106479555A (en) * | 2015-09-01 | 2017-03-08 | 江苏科创石化有限公司 | A kind of delayed coking anti-coking agent and preparation method thereof |
| CN106811247A (en) * | 2015-12-01 | 2017-06-09 | 廊坊富海添加剂有限公司 | A kind of new and effective composite antioxidant and preparation method thereof |
| CN108165295A (en) * | 2018-01-10 | 2018-06-15 | 广昌达新材料技术服务（深圳）股份有限公司 | A kind of liquid for oil refining process delayed coking increases income agent |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665287A (en) * | 2008-09-05 | 2010-03-10 | 华东电力试验研究院有限公司 | Scale inhibitor |
| CN104479729A (en) * | 2014-10-31 | 2015-04-01 | 中国海洋石油总公司 | Coke inhibiting liquid yield increasing agent for refinery coking delaying apparatus, and preparation method thereof |
| CN106479555A (en) * | 2015-09-01 | 2017-03-08 | 江苏科创石化有限公司 | A kind of delayed coking anti-coking agent and preparation method thereof |
| CN106811247A (en) * | 2015-12-01 | 2017-06-09 | 廊坊富海添加剂有限公司 | A kind of new and effective composite antioxidant and preparation method thereof |
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