CN113322095B - Ultrahigh-temperature slurry oil sedimentation agent and ultrahigh-temperature slurry oil ash removal method thereof - Google Patents
Ultrahigh-temperature slurry oil sedimentation agent and ultrahigh-temperature slurry oil ash removal method thereof Download PDFInfo
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- CN113322095B CN113322095B CN202110747152.8A CN202110747152A CN113322095B CN 113322095 B CN113322095 B CN 113322095B CN 202110747152 A CN202110747152 A CN 202110747152A CN 113322095 B CN113322095 B CN 113322095B
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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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
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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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
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- Chemical Kinetics & Catalysis (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses an ultrahigh temperature slurry oil sedimentation agent and a method for removing slurry oil ash at ultrahigh temperature. The invention relates to an ultrahigh temperature slurry oil sedimentation agent which is prepared by the following method: reacting phenol and formaldehyde for 3-8 h under the action of an acid catalyst at 30-100 ℃, adding an amine compound, continuously reacting for 4-10 h at 50-150 ℃, and decompressing and distilling water in a system after the reaction is finished to obtain a target product; the molar ratio of the phenol, formaldehyde and amine compounds is 1: (1-2.5): (0.1-3.5), the dosage of the acid catalyst is 0.01-3% of the mass of phenol; then preparing the ultra-high Wen Youjiang settling agent solution with the mass concentration of 20-60% by using a high boiling point mixed solvent and the synthesized amine modified phenolic resin. The slurry deashing technology has the advantages of strong raw material adaptability, short treatment time, low energy consumption and obvious treatment effect, and the slurry deashing rate can reach more than 98%.
Description
Technical Field
The invention belongs to the technical field of oil additives, and particularly relates to a novel ultrahigh Wen Youjiang sedimentation agent for oil slurry deashing and a method for removing oil slurry ash through ultrahigh temperature sedimentation treatment.
Background
With the continuous inferior and heavy crude oil properties, the processing difficulty of the catalytic cracking device is increased, the processing capability is ensured for maintaining the long-time safe and stable operation of the device, the refining ratio of the slurry oil is generally reduced, and the discharge amount of the external catalytic slurry oil is increased. It is counted that the catalytic cracking processing capacity of China is only inferior to the United states, and the catalytic cracking (FCC) slurry oil is used as one of main byproducts of a catalytic cracking device, and the yield is about 6-8% of the catalytic cracking processing capacity, namely about 9-12 Mt/a. The catalytic slurry oil is rich in 3-5 ring aromatic hydrocarbon, and is an ideal raw material for producing carbon black, needle coke and carbon fiber. However, because the catalytic slurry oil contains a large amount of solid particles such as catalyst powder and the like, the raw material requirement for producing high-quality needle coke cannot be met, so that the catalyst powder in the catalytic slurry oil is effectively removed, the ash content of the slurry oil is reduced, and the method has important significance for high value-added utilization of the slurry oil.
Because the solid particles in the FCC slurry oil have small particle size, the slurry oil has high viscosity and complex properties, so that the catalyst particles in the slurry oil are extremely difficult to remove. At present, the method for removing solid particles of FCC oil slurry mainly comprises a sedimentation method, a filtering method, a centrifugation method and an electrostatic separation method, and the four separation methods have respective advantages and disadvantages and cannot well solve the problem of removing solid of the oil slurry.
Patent CN106318440B discloses an oil slurry settling agent, which comprises the main components of 10.0-12.0% of polyoxyethylene polyoxypropylene block polymer, 80007.0-8.0% of PPG, 6.5% of dimethyl diallyl ammonium chloride homopolymer, 5.0% of polyoxyethylene sorbitan laurate and the balance of S-150 aromatic oil. When the addition amount of the sedimentation agent is 3-5% of the catalytic cracking slurry oil, the mixture is uniformly mixed, and the mixture is settled for 10-16 hours in a sedimentation tank at 90 ℃, and the ash removal rate of the slurry oil is between 60 and 90%.
Patent CN110938210a provides an ash content settling agent of end amino block polyether slurry oil and a preparation method thereof, and the settling agent utilizes the principle of combining the effect of destroying an electric double layer and the effect of bridging, and has good dispersibility in the slurry oil. The ash removal rate of the slurry oil after sedimentation treatment for 24 hours at 90 ℃ can reach more than 90%, and the ash content is reduced to below 0.02%.
Patent CN107849465A provides an oil slurry settling agent, which comprises the following components in percentage by weight: 10-50% of polymethacrylic resin, 5-30% of alkyl quaternary ammonium salt, 5-20% of alkoxy phenolic resin and 25-80% of solvent, and the sedimentation agent provided by the patent can reduce ash content in slurry oil to below 50 ppm.
Patent CN107794077A provides an oil slurry settling agent, which comprises the following components in percentage by weight: 70-80% of polyether, 15-25% of high flash point solvent and 1-10% of polypropylene glycol. The ash removal rate of the oil slurry using the settling agent reaches more than 90 percent.
Patent CN111621322a provides an oil slurry settling agent, which comprises the following main components: 0-40% of polyol polyether, 0-40% of polyol polyether ester, 0-10% of 1% concentration electroeliminating flocculant solution, aromatic hydrocarbon solvent oil and 0-100% of polyol. The ash removal rate of slurry oil of the settling agent is more than 90 percent.
Patent CN110964557a provides an oil slurry settling agent comprising 30 to 50 parts of diblock polyoxyethylene polyoxypropylene ether, 5 to 10 parts of diepoxide, 5 to 10 parts of isooctyl alcohol and 40 to 60 parts of solvent. After 24 hours of sedimentation, the ash content in the slurry oil can be reduced to the range of less than 0.1 percent, and the removal rate is more than 94 percent.
Although the oil slurry settling agent provided by the prior patent has obvious sound effect and the oil slurry deashing rate is up to more than 90%, the ash content of the oil slurry settling agent which can be used in actual factories is generally between 200 and 500ppm after the oil slurry is deashed, and the oil slurry settling agent provided by the prior patent carries out settling treatment at the temperature of about 100 ℃, the settling time is longer, and the adding amount is large, so that the oil slurry treatment cost is high. Therefore, the development of an effective slurry oil settling agent and slurry oil stripping method for improving the high-value utilization of slurry oil is a problem to be solved urgently at present.
Disclosure of Invention
The high-efficiency utilization of the slurry oil is limited due to the high content of the solid particles of the catalytic slurry oil, the current settling agent for the slurry oil has limited effect and long treatment time, and meanwhile, the slurry oil needs to be subjected to heat exchange operation before settling and solid removing treatment, and a settling tank still needs to be heated after the agent is added, so that more energy is consumed in the process. In order to effectively remove solid particles in the slurry oil and improve the comprehensive utilization value of the slurry oil, the invention provides a slurry oil sedimentation agent and an ultra-high Wen Youjiang sedimentation treatment process used under the ultra-high temperature condition, which can effectively reduce the ash content of the slurry oil and achieve the deashing effect.
Through research, the following findings are found: the temperature has a remarkable influence on the properties of the slurry oil, the viscosity of the slurry oil is obviously reduced along with the rise of the temperature, the colloid stability of the slurry oil is poor, and the change of the properties is beneficial to the sedimentation and removal of solid particles in the slurry oil. And FCC slurry oils are heavy byproducts of unconverted hydrocarbon composition at 343-593 c of the main fractionator bottoms of the FCC unit, so it is contemplated that the slurry oils may be subjected to ultra-high temperature settling at ultra-high temperatures in order to effectively reduce ash content of the slurry oils.
In order to achieve the above object, the present invention is specifically as follows:
the preparation process of superhigh temperature oil slurry settling agent consists of amine modified phenolic resin and mixed solvent with high boiling point, and the new oil slurry settling and depurating technology is to use the characteristic of high temperature of outer throwing oil slurry in superhigh temperature condition. The method specifically comprises the following steps:
1) Reacting phenol and formaldehyde for 3-8 h under the action of an acid catalyst at 30-100 ℃, adding an amine compound, continuously reacting for 4-10 h at 50-150 ℃, and decompressing and distilling water in a system after the reaction is finished to obtain a target product; the molar ratio of the phenol, formaldehyde and amine compounds is 1: (1-2.5): (0.1-3.5), the dosage of the acid catalyst is 0.01-3% of the mass of phenol;
2) And then preparing the amine modified phenolic resin synthesized in the step 1) into an ultra-high Wen Youjiang settling agent solution with the mass concentration of 20-60% by using a high-boiling mixed solvent with the boiling point of 200-400 ℃.
In the above technical solution, the amine compound in the step 1) is one or more of propylamine, butylamine, pentylamine, dimethylamine, diethylamine, diisopropylamine, isopropylamine, isobutylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, cyclohexylamine, aniline, N-methylaniline, 2-methyl-N-methylaniline, p-bromoaniline, melamine, and the like.
The acid catalyst in the step 1) is one or more of sulfuric acid, phosphoric acid, oxalic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like.
The invention also provides the superhigh Wen Youjiang sedimentation agent prepared by the preparation method.
The invention further provides a method for removing ash content of the slurry oil by carrying out ultra-high temperature sedimentation on the slurry oil by using the ultra-high Wen Youjiang sedimentation agent, the ultra-high Wen Youjiang sedimentation agent is mixed with the slurry oil thrown out from 200-400 ℃ and then pumped into a sedimentation tank for sedimentation treatment, and the ash content in the slurry oil after the treatment is reduced to 100 mug.g -1 In the process, the ash removal rate of the slurry reaches more than 98 percent.
Wherein, the superhigh Wen Youjiang sedimentation agent and the thrown slurry oil are uniformly mixed by a pipeline or are uniformly stirred and mixed in a mixing tank.
The usage amount of the ultra-high Wen Youjiang sedimentation agent is preferably 50-400 ppm.
The sedimentation treatment time is preferably 4 to 12 hours.
Compared with the prior art, the invention synthesizes the superhigh Wen Youjiang sedimentation agent, the decomposition temperature of the amine compound modified phenolic resin is about 400 ℃, and the invention is suitable for sedimentation treatment of oil slurry in a high-temperature environment. According to the invention, the ultra-high Wen Youjiang sedimentation treatment is carried out by utilizing the property characteristics of the catalytic device such as high temperature of the oil slurry thrown out from the catalytic device and the influence of the temperature on the property of the oil slurry and the solid particles, the viscosity of the oil slurry is greatly reduced, and the sedimentation speed and effect of the solid particles are greatly improved; the treatment process is simple, low in energy consumption, remarkable in solid removal effect, strong in raw material adaptability and wide in industrial application prospect.
Detailed Description
The present invention will be further described in detail with reference to the following examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1.
50g of phenol and 19.5g of formaldehyde solution with the concentration of 50% are added into a three-neck flask with an electric stirrer, a thermometer and a condenser, stirring is started after 10min, 0.5g of p-toluenesulfonic acid is added, the temperature is slowly raised to 75 ℃ and then the reaction is carried out for 3.5h, 45g of aniline is added after the reaction is finished and the temperature is raised to 140 ℃, and the reaction is continued for 5h. Finally, decompressing and steaming out water generated by the reaction in the system to obtain the phenolic resin modified by the aniline, wherein the decomposition temperature of the phenolic resin after modification reaches about 410 ℃. The mass ratio of SA-2000 and triethylene glycol which meet the requirements of GB/T29497-2017 is 1:1 is a mixed solvent, and the synthesized aniline modified phenolic resin is prepared into an ultra-high Wen Youjiang settling agent A with the concentration of 55 percent.
Example 2.
50g of phenol and 19.5g of formaldehyde solution with the concentration of 50% are added into a three-neck flask with an electric stirrer, a thermometer and a condenser tube, stirring is started, 0.3g of sulfuric acid is added after 10min, the temperature is slowly raised to 80 ℃ for reaction for 4h, 50g of melamine is added after the reaction is finished, the temperature is raised to 135 ℃, and the reaction is continued for 6h. Finally, decompressing and steaming out water generated by the reaction in the system to obtain the melamine modified phenolic resin, wherein the decomposition temperature of the modified phenolic resin reaches about 430 ℃. The heavy diesel oil with the distillation range of 350-410 ℃ and paraffin oil with the boiling point of 300-550 ℃ are mixed according to the mass ratio of 1:1 is a mixed solvent, and the synthesized melamine modified phenolic resin is prepared into an ultra-high Wen Youjiang sedimentation agent B with the concentration of 55 percent.
Example 3.
Two kinds of oil slurries from different refineries were selected as experimental oil slurries, the main physicochemical properties of which are shown in table 1.
Table 1 main performance parameters of experimental slurries
The experimental method comprises the following steps: the method provided by the invention is used for examining the ash removal efficiency of the slurry oil by changing the variables such as the sedimentation temperature, the sedimentation time and the consumption of the sedimentation agent, and determining the ash content according to the method specified in national standard GB/T508-85 ash determination method of petroleum products. The experimental results are shown in table 2.
TABLE 2 experimental results of the effect of ultra-high Wen Youjiang settling agent
As shown in the experimental results of Table 2, the ultrahigh Wen Youjiang sedimentation agent provided by the invention has obvious ash removal effect on slurry oil under ultrahigh temperature conditions, and the ash content of the slurry oil after treatment is reduced to 100 mug.g -1 In the process, the de-ashing rate is more than 98 percent. The slurry oil treatment technology provided by the invention has the advantages of strong raw material adaptability, short treatment time, low energy consumption, obvious ash removal effect and wide industrial application prospect.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (7)
1. A process for removing ash from oil slurry by superhigh-temp deposition of oil slurry with superhigh-temp oil slurry depositing agent includes such steps as mixing superhigh-temp Wen Youjiang depositing agent with 200-400 deg.C oil slurry, pumping it into depositing tank, depositing, and decreasing ash content to 100 [ mu ] g.g -1 In the process, the ash removal rate of the slurry oil reaches more than 98 percent;
the preparation method of the superhigh Wen Youjiang sedimentation agent comprises the following steps:
1) Reacting phenol and formaldehyde for 3-8 h under the action of an acid catalyst at 30-100 ℃, adding an amine compound, continuously reacting for 4-10 h at 50-150 ℃, and decompressing and distilling water in a system after the reaction is finished to obtain a target product; the molar ratio of the phenol, formaldehyde and amine compounds is 1: (1-2.5): (0.1-3.5), the dosage of the acid catalyst is 0.01-3% of the mass of phenol;
2) The amine modified phenolic resin synthesized in the step 1) is prepared into an ultra-high Wen Youjiang settling agent solution with the mass concentration of 20-60% by using a high boiling point mixed solvent with the boiling point of 200-400 ℃.
2. The method according to claim 1, wherein the ultra-high Wen Youjiang settling agent and the slurry are mixed uniformly by pipeline or stirred and mixed uniformly in a mixing tank.
3. The method according to claim 1, wherein the ultra-high Wen Youjiang sedimentation agent is used in an amount of 50 to 400ppm.
4. The method according to claim 1, wherein the sedimentation treatment time is 4 to 12 hours.
5. The method according to claim 1, wherein the amine compound is one or more of propylamine, butylamine, pentylamine, dimethylamine, diethylamine, diisopropylamine, isopropylamine, isobutylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, cyclohexylamine, aniline, N-methylaniline, 2-methyl-N-methylaniline, p-bromoaniline and melamine.
6. The method according to claim 1, wherein the acidic catalyst is one or more of sulfuric acid, phosphoric acid, oxalic acid, benzenesulfonic acid and p-toluenesulfonic acid.
7. The method according to claim 1, wherein the high boiling point mixed solvent is one of paraffin oil, high boiling point aromatic hydrocarbon solvent, diesel oil, heavy diesel oil, diethylene glycol, triethylene glycol, diphenyl ether and hexamethyl phosphonite.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1254849A (en) * | 1984-09-20 | 1989-05-30 | Exxon Research And Engineering Company | Process for the removal of solids from an oil |
| CN101346454A (en) * | 2005-12-23 | 2009-01-14 | 因诺斯佩克有限公司 | Process |
| CN104231197A (en) * | 2014-09-05 | 2014-12-24 | 中国海洋石油总公司 | Amido omodified phenolic resin and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1254849A (en) * | 1984-09-20 | 1989-05-30 | Exxon Research And Engineering Company | Process for the removal of solids from an oil |
| CN101346454A (en) * | 2005-12-23 | 2009-01-14 | 因诺斯佩克有限公司 | Process |
| CN104231197A (en) * | 2014-09-05 | 2014-12-24 | 中国海洋石油总公司 | Amido omodified phenolic resin and preparation method thereof |
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