A method for treating catalytic slurry oil

Abstract

The present invention relates to the technical field of petrochemical industry, and specifically relates to a method for treating catalytic slurry. In the present invention, an amino-epoxy reaction occurs between the amino phosphonic acid resin / nickel and palladium epoxy succinate, as well as a similar reaction between 2'-amino-[1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid palladium and palladium epoxy succinate, to form a resin-supported palladium / nickel ion complex; during the hydrogenation process, the resin-supported palladium / nickel ion complex is reduced by hydrogen to be reduced into a hydrogenation catalyst of supported palladium / nickel elements; the hydrogenation catalyst of supported palladium / nickel elements plays a catalytic role in the hydrogenation reaction, and the hydrogenation activity of palladium and nickel elements is relatively high, which can effectively convert the carbon-carbon double bonds in the oil into single bonds, thereby improving the catalytic effect, promoting the hydrogenation reaction of the oil, and increasing the hydrogenation yield.

Description

Technical Field

[0001] The present invention relates to the technical field of petrochemical engineering, and particularly to a method for treating catalytic slurry. Background Art

[0002] Catalytic slurry is a by-product with extremely special properties generated during the heavy oil FCC process. Due to its high density, large relative molecular mass, high viscosity, and containing a large amount of fine particulate catalysts, its utilization is restricted. Currently, catalytic slurry is generally sold as a blending component of heavy fuel oil. Not only is its utilization value low, but the catalyst fines in it will cause wear of the burner nozzles of the furnace, resulting in serious ash accumulation on the surface of the furnace tubes and a decrease in thermal efficiency, affecting the stable operation of the furnace. Therefore, the problem of the outlet of catalytic slurry has been plaguing refinery enterprises for many years. With the heavyweight of FCC feedstock, the output of catalytic slurry is increasing, and it is particularly important to solve its outlet problem.

[0003] Chinese Patent CN112745928A: discloses a method for treating catalytic slurry, which successively includes the following steps: The first step: molecular distillation pretreatment program, introducing catalytic slurry into a primary molecular distiller to collect light component oil and heavy component oil; The second step: hydrotreating pretreatment program, heating the light component oil to remove metal impurities and oxides therein to obtain hydrotreated oil; The third step: hydroaromatic saturation and cracking program, the fraction of the hydrotreated oil with a distillation range ≥ 360 °C after treatment is contacted with a hydrotreating catalyst to saturate its aromatic rings and partially crack to obtain a mixed hydrogenated oil; The fourth step: supplementary refining program, the fraction of the mixed hydrogenated oil with a distillation range ≥ 360 °C after treatment is again contacted with a hydrotreating catalyst under high temperature and high pressure to saturate all olefins in the oil product to obtain catalytic hydrogenated oil; The fifth step: fractionation program, finally obtaining environmentally friendly aromatic oil.

[0004] Chinese Patent CN101608128A: discloses a new process for treating catalytic slurry in a refinery, belonging to the technical field of heavy oil treatment in petrochemical engineering. The new process for treating catalytic slurry in a refinery is carried out according to the following steps: (1) loading the catalytic slurry treated as waste in the refinery into a reaction tank, adding furfural and benzenesulfonic acid to make the catalytic slurry settle and separate; (2) subjecting the separated clarified oil to three-stage separation by the fractionation method of the existing technology; (3) oxidizing the asphaltic resinous substance to obtain heavy traffic asphalt raw materials of No. 70 and No. 50 for high-grade highways.

[0005] Chinese Patent CN207793179U: It relates to the field of petroleum processing and discloses a catalytic slurry treatment device. The device includes: a feed heating unit (1), a vacuum distillation unit, and an oxidation treatment unit connected in sequence through pipelines. The feed heating unit (1) is used to heat a mixed material containing catalytic slurry and vacuum residue; the vacuum distillation unit is used to perform vacuum distillation on the mixed material heated by the feed heating unit (1); the oxidation treatment unit is used to perform oxidation treatment on the heavy components obtained by vacuum distillation in the vacuum distillation unit.

[0006] However, in the above patent and the prior art, the sedimentation and purification separation effects of catalytic slurry are poor, and it is difficult to remove ash; traditional filters need to be frequently switched for backwashing, and the filter elements are prone to clogging, difficult to clean, have high maintenance and operation costs, and are not easy to operate, etc. Summary of the Invention

[0007] In view of the deficiencies of the prior art, the present invention provides a method for treating catalytic slurry. The supported palladium / nickel element hydrogenation catalyst disclosed in the present invention plays a catalytic role in the hydrogenation reaction. The hydrogenation activities of palladium and nickel elements are relatively high, which can effectively convert the carbon-carbon double bonds in the oil into single bonds, thereby improving the catalytic effect, promoting the hydrogenation reaction of the oil, and increasing the hydrogenation yield.

[0008] To achieve the above objectives, the present invention is realized through the following technical solutions:

[0009] A method for treating catalytic slurry, and its operation steps are as follows:

[0010] S1: Weigh 70 - 90 parts of catalytic slurry by weight. After heating and raising the temperature, add 0.01 - 0.1 part of demulsifier, 0.5 - 3 parts of flocculant, and 5 - 10 parts of glucose aqueous solution, stir and mix, pour it into a settling tube for sedimentation, and filter it through a high-temperature ceramic membrane after sedimentation;

[0011] S2: Use a hydrogenation treatment resin catalyst to perform hydrorefining on the filtrate of S1 at 200 - 240 °C, and the hydrogenated oil is subjected to vacuum distillation;

[0012] Preferably, the hydrogen-oil volume ratio during the hydrorefining process is 800 - 1600:1;

[0013] Preferably, the hydrogen-oil volume space velocity during the hydrorefining process is 0.1 - 2 / h;

[0014] Preferably, the hydrogen partial pressure during the hydrorefining process is 10 - 20 MPa.

[0015] Preferably, S1 is heated to 70 - 100 °C.

[0016] Preferably, the mass fraction of the glucose aqueous solution in S1 is 20-30%.

[0017] Preferably, the stirring and mixing time of S1 is 10-30 min.

[0018] Preferably, the sedimentation time of S1 is 8-15 h.

[0019] Preferably, the demulsifier of S1 is one of polyoxyethylene polyoxypropylene octadecanol ether and polyoxyethylene polyoxypropylene polyether.

[0020] Preferably, the flocculant of S1 is one of sodium polyacrylate, polyaluminum chloride, polyacrylamide, polymeric aluminum ferric silicate, ferric trichloride, and polyvinyl alcohol.

[0021] Preferably, the preparation method of the hydrotreating resin catalyst is as follows:

[0022] A1: By weight, add 1000-1500 parts of nickel nitrate aqueous solution with a concentration of 0.05-0.5 mol / L to the first reaction kettle, then add 100-120 parts of aminophosphonic acid resin, stir at 30-40 °C for 10-30 h, then filter, wash, and dry to obtain the first product;

[0023] A2: By weight, add 0.5-1.5 parts of palladium chloride, 0.03-0.06 parts of 2'-amino-[1,1':4',1″-terphenyl]-4,4″-dicarboxylic acid, and 1000-1500 parts of ethanol to the second reaction kettle, stir at 30-40 °C for 20-50 h, then add 6-12 parts of epoxy succinic acid, stir at 60-70 °C for 60-100 minutes, then add 100-160 parts of the first product and 2-5 parts of potassium hydroxide, keep warm and stir for 100-140 minutes, then filter, wash, and vacuum dry to obtain the hydrotreating resin catalyst.

[0024] Preferably, the addition ratio of the hydrotreating resin catalyst is: 10-20% by volume of the hydrofining reactor.

[0025] Preferably, the aminophosphonic acid resin is such as Purolite S940

[0026]

[0027] Reaction mechanism

[0028] First, an amino-epoxy reaction occurs between the amino phosphonic acid resin / nickel and palladium epoxybutanedioate, as well as between palladium 2'-amino-[1,1':4',1''-terphenyl]-4,4''-dicarboxylate and palladium epoxybutanedioate, to obtain a palladium / nickel ion complex immobilized on the resin through complexation. Subsequently, during the hydrogenation process, it is reduced to a hydrogenation catalyst of palladium / nickel elements immobilized on the resin by hydrogen, and this hydrogenation catalyst can improve the hydrogenation yield.

[0029] An amino-epoxy reaction occurs between the amino phosphonic acid resin / nickel and palladium epoxybutanedioate, as well as a similar reaction between palladium 2'-amino-[1,1':4',1''-terphenyl]-4,4''-dicarboxylate and palladium epoxybutanedioate, to form a palladium / nickel ion complex immobilized on the resin. During the hydrogenation process, the palladium / nickel ion complex immobilized on the resin is reduced by hydrogen to a hydrogenation catalyst of immobilized palladium / nickel elements. The hydrogenation catalyst of immobilized palladium / nickel elements plays a catalytic role in the hydrogenation reaction. The hydrogenation activities of palladium and nickel elements are relatively high, and they can effectively convert the carbon-carbon double bonds in the oil into single bonds, thereby increasing the hydrogen yield of the oil. The palladium / nickel catalyst immobilized on the resin has good stability and reusability, which can reduce the loss and cost of the catalyst. The amino phosphonic acid resin can complex palladium and nickel ions, enhance the dispersibility and stability of the catalyst, and improve the catalytic effect. It promotes the hydrogenation reaction of the oil and increases the hydrogenation yield.

[0030] Technical effects

[0031] A method for treating catalytic slurry according to the present invention has the following remarkable effects compared with the prior art:

[0032] 1. The method for treating catalytic slurry of the present invention adopts the method of demulsification - flocculation sedimentation, which can effectively remove the catalyst powder in the slurry and reduce the ash content in the slurry;

[0033] 2. The method for treating catalytic slurry of the present invention adopts high-temperature ceramic membrane filtration, which has the characteristics of high filtration accuracy, does not require frequent switching of filters, the filter element is not easily blocked and is convenient to clean; and the operation is relatively simple and easy to industrialize. Specific embodiments

[0034] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0035] The test methods involved in the embodiments of the present invention are referred to as follows:

[0036] The ash content is determined with reference to "Method for Determination of Ash in Petroleum Products" (GB / T508 - 85).

[0037] Example 1

[0038] A method for treating catalytic slurry oil, the operation steps of which are as follows:

[0039] S1: Weigh 70 g of catalytic slurry oil. After heating and raising the temperature, add 0.01 g of demulsifier, 0.5 g of flocculant, and 5 g of glucose aqueous solution, stir and mix, pour it into a settling tube for sedimentation, and after sedimentation, filter it through a high-temperature ceramic membrane;

[0040] S2: Use a hydrotreating resin catalyst to carry out hydrofining on the filtrate of S1 at 200 °C, and the hydrotreated oil is subjected to vacuum distillation; the volume ratio of hydrogen to oil during the hydrofining process is 800:1;

[0041] The volume space velocity of hydrogen to oil during the hydrofining process is 0.1 / h;

[0042] The hydrogen partial pressure during the hydrofining process is 10 MPa.

[0043] Heat S1 to 70 °C.

[0044] The mass fraction of the glucose aqueous solution in S1 is 20%.

[0045] The stirring and mixing time in S1 is 10 min.

[0046] The sedimentation time in S1 is 8 h.

[0047] The demulsifier in S1 is polyoxyethylene polyoxypropylene octadecanol ether.

[0048] The flocculant in S1 is sodium polyacrylate.

[0049] The preparation method of the above-mentioned hydrotreating resin catalyst:

[0050] A1: Add 1000 g of nickel nitrate aqueous solution with a concentration of 0.05 mol / L to the first reaction kettle, then add 100 g of amino phosphonic acid resin, stir at 30 °C for 10 h, then filter, wash, and dry to obtain the first product;

[0051] A2: Add 0.5 g of palladium chloride, 0.03 g of 2'-amino-[1,1':4',1″-terphenyl]-4,4″-dicarboxylic acid, and 1000 g of ethanol to the second reaction kettle, stir at 30 °C for 20 h, then add 6 g of epoxy succinic acid, stir at 60 °C for 60 minutes, then add 100 g of the first product and 2 g of potassium hydroxide, keep warm and stir for 100 minutes, then filter, wash, and dry under vacuum to obtain the hydrotreating resin catalyst.

[0052] The addition ratio of the above-mentioned hydrotreating resin catalyst is: 10% by volume of the hydrofining reactor.

[0053] The amino phosphonic acid resin such as Purolite S940

[0054]

[0055] Example 2

[0056] A method for treating catalytic oil slurry, the operation steps of which are as follows:

[0057] S1: Weigh 75 g of catalytic oil slurry, after heating and raising the temperature, add 0.05 g of demulsifier, 1 g of flocculant, 6 g of glucose aqueous solution, stir and mix, pour it into a settling tube for sedimentation, and filter it through a high-temperature ceramic membrane after sedimentation;

[0058] S2: Use a hydrotreating resin catalyst to carry out hydrofining on the filtrate of S1 at 210 °C, and the hydrotreated oil is subjected to vacuum distillation; the volume ratio of hydrogen to oil during the hydrofining process is 1000:1;

[0059] The volume space velocity of hydrogen to oil during the hydrofining process is 1 / h;

[0060] The hydrogen partial pressure during the hydrofining process is 15 MPa.

[0061] Heat S1 to 80 °C.

[0062] The mass fraction of the glucose aqueous solution in S1 is 25%.

[0063] The stirring and mixing time of S1 is 15 min.

[0064] The sedimentation time of S1 is 10 h.

[0065] The demulsifier in S1 is polyoxyethylene polyoxypropylene octadecanol ether.

[0066] The flocculant in S1 is polyaluminum chloride.

[0067] The preparation method of the hydrotreating resin catalyst:

[0068] A1: Add 1100 g of nickel nitrate aqueous solution with a concentration of 0.2 mol / L to the first reaction kettle, then add 105 g of amino phosphonic acid resin, stir at 35 °C for 15 h, then filter, wash, and dry to obtain the first product;

[0069] A2: Add 0.8 g of palladium chloride, 0.04 g of 2'-amino-[1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid, and 1100 g of ethanol to the second reaction kettle, stir at 35 °C for 30 h, then add 8 g of epoxy succinic acid, stir at 68 °C for 70 minutes, then add 120 g of the first product and 3 g of potassium hydroxide, keep warm and stir for 110 minutes, then filter, wash, and dry under vacuum to obtain the hydrotreating resin catalyst.

[0070] The addition ratio of the hydrotreating resin catalyst is: 15% by volume of the hydrofining reactor.

[0071] The amino phosphonic acid resin is such as Purolite S940

[0072]

[0073] Example 3

[0074] A method for treating catalytic slurry oil, the operation steps of which are as follows:

[0075] S1: Weigh 85 g of catalytic slurry oil. After heating and raising the temperature, add 0.08 g of demulsifier, 2 g of flocculant, and 8 g of glucose aqueous solution, stir and mix, pour it into a settling tube for sedimentation, and filter it through a high-temperature ceramic membrane after sedimentation;

[0076] S2: Use a hydrotreating resin catalyst to carry out hydrofining on the filtrate of S1 at 230 °C, and the hydrogenated oil is subjected to vacuum distillation; the volume ratio of hydrogen to oil during the hydrofining process is 1400:1;

[0077] The volume space velocity of hydrogen to oil during the hydrofining process is 1.5 / h;

[0078] The partial pressure of hydrogen during the hydrofining process is 15 MPa.

[0079] Heat S1 to 90 °C.

[0080] The mass fraction of the glucose aqueous solution in S1 is 25%.

[0081] The stirring and mixing time of S1 is 25 min.

[0082] The sedimentation time of S1 is 13 h.

[0083] The demulsifier in S1 is polyoxyethylene polyoxypropylene polyether.

[0084] The flocculant in S1 is polyacrylamide.

[0085] The preparation method of the hydrotreating resin catalyst:

[0086] A1: Add 1400 g of nickel nitrate aqueous solution with a concentration of 0.4 mol / L to the first reaction kettle, then add 115 g of amino phosphonic acid resin, stir at 35 °C for 25 h, then filter, wash, and dry to obtain the first product;

[0087] A2: Add 1.3 g of palladium chloride, 0.05 g of 2'-amino-[1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid, and 1400 g of ethanol into the second reactor, stir at 35 °C for 40 h, then add 10 g of epoxy succinic acid, stir at 65 °C for 90 minutes, then add 150 g of the first product and 4 g of potassium hydroxide, stir while maintaining the temperature for 130 minutes, then filter, wash, and dry under vacuum to obtain the hydrotreating resin catalyst.

[0088] The addition ratio of the hydrotreating resin catalyst is: 15% by volume of the hydrofining reactor.

[0089] The amino phosphonic acid resin is such as Purolite S940

[0090]

[0091] Example 4

[0092] A method for treating catalytic slurry, the operation steps are as follows:

[0093] S1: Weigh 90 g of catalytic slurry, after heating and raising the temperature, add 0.1 g of demulsifier, 3 g of flocculant, and 10 g of glucose aqueous solution, stir and mix, pour into the settling tube for sedimentation, and filter through a high-temperature ceramic membrane after sedimentation;

[0094] S2: Use the hydrotreating resin catalyst to carry out hydrofining on the filtrate of S1 at 240 °C, and the hydrogenated oil is subjected to vacuum distillation; the hydrogen-oil volume ratio during the hydrofining process is 1600:1;

[0095] The hydrogen-oil volume space velocity during the hydrofining process is 2 / h;

[0096] The hydrogen partial pressure during the hydrofining process is 20 MPa.

[0097] Heat S1 to 100 °C.

[0098] The mass fraction of the glucose aqueous solution in S1 is 30%.

[0099] The stirring and mixing time of S1 is 30 min.

[0100] The sedimentation time of S1 is 15 h.

[0101] The demulsifier in S1 is polyoxyethylene polyoxypropylene polyether.

[0102] The flocculant in S1 is polyvinyl alcohol.

[0103] The preparation method of the hydrotreating resin catalyst:

[0104] A1: Add 1500 g of nickel nitrate aqueous solution with a concentration of 0.5 mol / L into the first reactor, then add 120 g of amino phosphonic acid resin, stir at 40 °C for 30 h, then filter, wash, and dry to obtain the first product;

[0105] A2: Add 1.5 g of palladium chloride, 0.06 g of 2'-amino-[1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid, and 1500 g of ethanol into the second reactor, stir at 40 °C for 50 h, then add 12 g of epoxy succinic acid, stir at 70 °C for 100 minutes, then add 160 g of the first product and 5 g of potassium hydroxide, keep stirring at a constant temperature for 140 minutes, then filter, wash, and dry under vacuum to obtain the hydrotreating resin catalyst.

[0106] The addition ratio of the hydrotreating resin catalyst is: 20% by volume of the hydrofining reactor.

[0107] The amino phosphonic acid resin is such as Purolite S940

[0108]

[0109] Blank sample

[0110] In this example, the hydrotreating resin catalyst is not added, and the others are the same as in Example 1.

[0111] Comparative Example 1

[0112] In this example, the amino phosphonic acid resin is not added, and the others are the same as in Example 1.

[0113] Comparative Example 2

[0114] In this example, 2'-amino-[1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid is not added, and the others are the same as in Example 1.

[0115] Comparative Example 3

[0116] In this example, epoxy succinic acid is not added, and the others are the same as in Example 1.

[0117] Test results:

[0118] Ash content (μg / g) Hydrogenation yield (%) Example 1 83 97.36 Example 2 76 97.84 Example 3 65 98.29 Example 4 59 98.85 Blank sample 3887 73.62 Comparative example 1 293 85.21 Comparative example 2 187 89.37 Comparative example 3 155 91.53

[0119] Through the data analysis of the above examples and comparative examples, the treatment method of catalytic slurry of the present invention can effectively reduce the ash content in the slurry and improve the hydrogenation yield.

[0120] The above are only the preferred embodiments of the present invention and do not impose any form of limitation on the present invention. Although the present invention has been disclosed above with the preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to equivalent embodiments with equivalent changes within the scope of the technical solution of the present invention. However, as long as it does not depart from the content of the technical solution of the present invention, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A method for treating catalytic slurry oil, the operation steps of which are as follows: S1: Weigh 70 - 90 parts by weight of catalytic slurry oil. After heating and raising the temperature, add 0.01 - 0.1 part of demulsifier, 0.5 - 3 parts of flocculant, and 5 - 10 parts of glucose aqueous solution, stir and mix, pour it into a settling tube for sedimentation, and after sedimentation, filter it through a high-temperature ceramic membrane; S2: Use a hydrotreating resin catalyst to carry out hydrorefining on the filtrate of S1 at 200 - 240 °C, and the hydrogenated oil is subjected to vacuum distillation; In the hydrorefining process, the hydrogen - to - oil volume ratio is 800 - 1600:1; In the hydrorefining process, the hydrogen - to - oil volume space velocity is 0.1 - 2 / h; In the hydrorefining process, the hydrogen partial pressure is 10 - 20 MPa; The preparation method of the above - mentioned hydrotreating resin catalyst: A1: Add 1000 - 1500 parts by weight of nickel nitrate aqueous solution with a concentration of 0.05 - 0.5 mol / L to the first reaction kettle, then add 100 - 120 parts of aminophosphonic acid resin, stir at 30 - 40 °C for 10 - 30 h, then filter, wash, and dry to obtain the first product; A2: Add 0.5 - 1.5 parts by weight of palladium chloride, 0.03 - 0.06 parts of 2’ - amino - [1,1’:4’,1″ - terphenyl] - 4,4″ - dicarboxylic acid, and 1000 - 1500 parts of ethanol to the second reaction kettle, stir at 30 - 40 °C for 20 - 50 h, then add 6 - 12 parts of epoxy succinic acid, stir at 60 - 70 °C for 60 - 100 minutes, then add 100 - 160 parts of the first product, 2 - 5 parts of potassium hydroxide, keep warm and stir for 100 - 140 minutes, then filter, wash, and vacuum - dry to obtain the hydrotreating resin catalyst.

2. The treatment method of catalytic slurry oil according to claim 1, wherein: In S1, heat it to 70 - 100 °C.

3. The treatment method of catalytic slurry according to claim 1, characterized in that: The mass fraction of the glucose aqueous solution in S1 is 20 - 30%.

4. A method for treating catalytic slurry oil according to claim 1, characterized in that: The stirring and mixing time in S1 is 10 - 30 min.

5. The treatment method of catalytic slurry oil according to claim 1, characterized in that: The sedimentation time in S1 is 8 - 15 h.

6. The method for treating catalytic slurry oil according to claim 1, characterized in that: The demulsifier in S1 is one of polyoxyethylene polyoxypropylene octadecanol ether and polyoxyethylene polyoxypropylene polyether.

7. A method for treating catalytic slurry oil according to claim 1, characterized in that: The flocculant in S1 is one of sodium polyacrylate, polyaluminum chloride, polyacrylamide, polymeric aluminum ferric silicate, ferric trichloride, and polyvinyl alcohol.

8. A method for treating catalytic slurry oil according to claim 1, characterized in that: The addition ratio of the above - mentioned hydrotreating resin catalyst is 10 - 20% of the volume percentage of the hydrorefining reactor.

9. A method for treating catalytic slurry oil according to claim 1, characterized in that: The aminophosphonic acid resin is PuroliteS940.

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