CN1632070A - A kind of residual oil suspended bed hydrogenation catalytic promoter and its application - Google Patents

Abstract

Disclosed is a suspended bed hydrogenation catalyst assistant belongs to the fields of oil procession and oil chemical technology. The assistant contains are or the combination of several ones willingly chosen from high molecule, synthesis organic high molecule, natural surface active agent, synthesis surface active agent, condensed aromatics, organic alcohol, organic carboxylate surfactant, organic carboxylic acid amide, organic carboxylic acid halogen, organic phosphide. It can be applied in the course of suspended bed hydrogenation, as well as that of hydrogenation mixing of hydrogenation and liquidifying coal. By adding the assistant, the hydrogenation effect of catalyst can be increased, as well as decreasing scale formation in reactor in the time of decreasing scale formation in fractional distillation part of the reacting pipe.

Description

A kind of residual oil suspended bed hydrogenation catalytic promoter and its application

Technical field:

The invention relates to a catalytic assistant in the hydrogenation process of a suspended bed of residual oil, and belongs to the technical fields of petroleum processing and petrochemical industry. The additive can be used in the hydrogenation process of residual oil suspension bed, and can also be used in the hydrogenation co-refining process of residual oil and coal, residual oil and waste plastic, residual oil and waste rubber, waste plastic and waste rubber, and coal liquefaction process. The catalytic promoter helps to improve the coke suppression effect of the catalyst in hydrogenation, and more importantly, it is beneficial to suppress the amount of coking in the reactor during the above process, and at the same time reduce the coking and coking in the heating furnace tube, reaction pipeline, fractionation and other parts. fouling phenomenon.

Background technique:

With the increasingly heavy oil produced and the increasing demand for light oil products in the market, people's demand for the technology of lightening heavy and residual oil is increasing day by day. Among the many residual oil processing technologies, the suspended bed hydrocracking process of residual oil has been paid more and more attention. The hydrogenation of suspended bed residual oil is to allow the residual oil to undergo thermal cracking and hydrogenation reactions in the presence of hydrogen and hydrogenation catalysts, thereby It can combine the characteristics of thermal processing and hydrogenation. Because it has many advantages such as high conversion rate, simple process, low equipment investment, high diesel yield and low coke production rate, the application prospect is extremely broad.

The existing residual oil suspended bed catalysts mainly include:

(1) The process of adding solid particle catalysts, such as the suspension bed hydrogenation technology in Germany in the early 1950s, which used ferrous sulfate on lignite for coal tar hydrogenation, but its hydrogenation activity was very low. Later, the combined cracking process (VCC) developed by German VEBA Company on the basis of coal and coal tar hydrogenation technology is a high-conversion thermal cracking process. The lignite and coke used as additives are ground to form oil with residue raw materials. The slurry is preheated together after adding new hydrogen and circulating gas, and enters the liquid phase reactor upstream, and is transformed in a one-pass manner at 440-485°C and a pressure of 25MPa. After the reaction product is separated, the residue which accounts for about 6% of the total feed mass fraction and contains 50% of solids is discharged. In the 1970s, the Canadian Mineral and Energy Technology Center began to develop the CHANMET hydrocracking process in response to the need for oil sand bitumen upgrading, and in 1985 a scale-up experiment was carried out at the Montreal refinery in Canada. The main feature of this process is that ferrous sulfate and pulverized coal are used as additives after grinding, and the mass fraction of the added amount is about 1% to 3%. The raw oil and circulating hydrogen mixed with additives are heated to the reaction temperature in respective heating furnaces. In order to prevent oil from coking in the furnace tube, a small amount of circulating hydrogen is injected into the furnace inlet. The oil and hydrogen heated to the reaction temperature are injected into the bottom of the reactor, and the reaction is carried out at 435-455° C. and about 14 MPa, and the mass conversion rate can reach 90%. CAMNET believes that adding FeSO ₄ -loaded coal powder with a particle size of about 100 meshes to the residual oil as an anti-coking agent can significantly reduce the formation of coke and coke precursors. They also use flue dust from coal-fired or oil-fired power plants as an anti-coking agent, adding 1% mass fraction to residual oil, hydrogenation at 10.3MPa, 450°C, when 524°C + conversion rate is 51.7%, desulfurization When the rate is 31.5%, the coke rate is significantly lower than that of the blank control sample. The researchers of the Canadian Minerals and Energy Technology Center also believe that after coal powder with a particle size of less than 60 meshes is loaded with more than 10% of Fe, Co, Mo, Zn and other metal salts, it can be used as a suspension bed hydrocracking process under a pressure of 1.4-24MPa. Anti-scorch agents work well.

In 1991, Petro-Canada proposed to use petroleum coke powder and iron sulfate anti-scorch agent for the suspension bed hydrogenation of residual oil. They mixed the crushed coke pieces crushed to 8-16 mesh with iron sulfate and heavy oil at a ratio of 35:15:50, and then ground them in a ball mill until the iron salt and coke powder particles were all smaller than 200 mesh, most of which were smaller than 30um . When this anti-coking agent is used for slag-reducing suspension bed hydrogenation, when the reaction pressure is 13.9MPa and the temperature is 450°C, the pitch conversion rate (basically no coking) can reach 88%. The conversion rate of asphalt is only 75% when coking agent. The HDH process researched and developed by Venezuelan INTEVEP company uses natural mineral fine powder containing Ni and V as a catalyst to carry out hydrogenation and upgrading of residual oil. The process is similar to the aforementioned suspension bed hydrogenation. The typical operating conditions are: reaction temperature 420-470°C, reaction pressure 7-14MPa, space velocity 0.3-1.0h ^-1 , gas-liquid ratio 1000-5000Nm ³ /m ³ , catalyst The mass fraction of the added amount is 2% to 5%. When processing different raw materials, the conversion rate is 85%-90%, the coke yield rate is 1.3%-2.3%, and the gas mass yield rate is 9.8%-10.2%. The reaction product passes through the hot separator to separate the liquid product, and the hot bottom stream containing the spent catalyst enters the catalyst separation system. The unconverted tail oil is separated from the catalyst, and the separated waste catalyst is discharged after being dried and incinerated.

(2) Homogeneous catalysts include oil-soluble organometallic catalysts and water-soluble catalysts. These two catalysts exist in the form of metal particles and their sulfides during the reaction, so they are not homogeneous catalysts in the sense of colloid chemistry. The Canadian (HC) ₃ technology is the representative of residual oil suspension bed hydrogenation with oil-soluble metal catalysts. Hydrogenation of residual oil with water-soluble catalyst suspension bed includes Exxon's technology using phosphomolybdic acid as a catalyst, and Chevron's technology using ammonium molybdate as a catalyst.

(3) Compound type catalysts, for example, the French Petroleum Research Institute compounded molybdenum naphthenate and cobalt naphthenate, and Exxon’s compound of iron oxide and cobalt phenolcyanine was used for hydrogenation of suspended bed residual oil. When the mass fraction of iron oxide is 7%, and the amount of cobalt is 400μg·g ^-1 , the coke formation rate can be reduced from 6.8% without anti-scorch agent to 0.4%. In addition to using various oil-soluble metal compounds directly in the suspension bed, there are also methods of using them in conjunction with various solid powders. In the 1970s, Exxon added 350-500 μg/g (calculated as metal) molybdenum naphthenate and iron oxide powder with a mass fraction of about 1% (calculated as iron) to the residual oil feed. , hydrogenation under 13.7MPa, the amount of coke is basically below 0.5%. And the catalyst can be filtered out and used repeatedly. After the cycle is normal, only about 1/6 of the new catalyst needs to be added. They later proposed molybdenum naphthenate on stainless steel powder as a catalyst for hydrogenation in a suspended bed.

Nobuum itum Ohtabe proposed to add molybdenum naphthenate or other ultrafine solid particles into the residual oil and stir evenly for hydrocracking. When the amount of organic acid metal salt is 300-1000 μg/g and the mass fraction of superfine solid particles is 2%-10%, the conversion rate at 520°C can reach 70%-80%.

Exxon company also used _CrO3 to react with alcohol to obtain oil-soluble di-tert-butyl chromate. This catalyst was used for the suspension bed hydrogenation of heavy Arabian slag reduction, and the reaction was carried out at 14.4MPa and 443°C. The catalyst addition amount was At 350μg/g, 524℃+conversion rate is 84.6%, coke formation rate is 1.43%

No matter what kind of catalyst is used, because the residual oil suspension bed hydrogenation process is carried out at a high temperature of 430-470 °C, the coking phenomenon of the residual oil is relatively serious, especially the coking phenomenon of the reactor during continuous operation at high temperature is serious, and this problem has always affected The process of industrialization of the process. In order to extend the continuous working cycle, reducing coking in the reactor during continuous operation at high temperature has undoubtedly become the focus of solving this problem.

Invention content:

The purpose of the present invention is to develop a kind of catalyst auxiliary agent of residual oil suspension bed hydrogenation, add a small amount of this auxiliary agent, can improve the hydrogenation coke suppressing effect of residue oil suspension bed hydrogenation catalyst on the one hand, on the other hand and more The important thing is to reduce the coking phenomenon in the continuous operation of the residual oil suspended bed hydrogenation reactor at high temperature, thereby greatly prolonging the start-up period of the residual oil suspended bed hydrogenation unit.

The object of the present invention is achieved in this way, aiming at the residual oil suspended bed hydrogenation process, develop a kind of residual oil suspended bed hydrogenation catalyst auxiliary agent, it is characterized in that this auxiliary agent contains natural organic macromolecule, synthetic organic macromolecule, natural surface Active agents, synthetic surfactants, condensed ring aromatic hydrocarbons, organic alcohols, organic carboxylic acids, organic carboxylates, organic carboxylic acid amides, organic carboxylic acid halides, organic phosphides, or any two or any of them For the combination of two or more, the added amount is 10-8000 μg/g of the residual oil raw material.

The catalyst additive can not only be used in the hydrogenation process of residual oil suspension bed, but also can be used in the hydrogenation co-refining process of residual oil and coal, residual oil and waste plastic, residual oil and waste rubber, waste plastic and waste rubber, and coal liquefaction process. The additive can improve the hydrogenation coke suppression effect of the hydrogenation catalyst, reduce the amount of coking in the continuous operation of the hydrogenation reactor at high temperature, and reduce the fouling in the reaction pipeline, fractionation and other parts, thereby greatly prolonging the hydrogenation process. The start-up period of the hydrogen plant.

Detailed ways:

The present invention will be described in detail below in conjunction with the examples.

The present invention aims at the hydrogenation process of residual oil suspension bed, and develops a hydrogenation catalyst additive, which contains one or any two or any combination of more than two of the following substances: natural organic polymers, synthetic organic polymers , natural surfactants, synthetic surfactants, condensed ring aromatics, organic alcohols, organic carboxylic acids, organic carboxylates, organic carboxylic acid amides, organic carboxylic acid halides, and organic phosphides, the amount of which is 1% of residual oil raw materials 10～8000μg/g. Natural organic polymers or synthetic organic polymers are natural starch, cellulose, polyethylene glycol, polycondensates of ethylene terephthalate, polycondensates of ethylenediamine terephthalate, and polycondensations of other dibasic carboxylic acid glycols Products and other dicarboxylic acid diamine polycondensates, including the above-mentioned natural or synthetic polymer modified products, polyacrylamide, polyacrylonitrile, partially hydrolyzed polyacrylamide, phenolic resin and their derivatives, Also includes polyethylene, polypropylene, polystyrene and their modifications and derivatives. The molecular weight range of the natural organic polymer or synthetic organic polymer is 100-20,000,000. The surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, cationic-nonionic amphoteric surfactants, and anionic-nonionic amphoteric surfactants. The anionic surfactant refers to alkylbenzenesulfonic acid series, alkylbenzenesulfonate series, alkylnaphthalenesulfonic acid series, alkylnaphthalenesulfonate series, organic sulfate series, organic phosphate series, organic fatty acids series, sulfonated lignite and sulfonated bitumen and their derivatives, petroleum sulfonate, lignin sulfonate. The cationic surfactants include organic quaternary ammonium salt series, organic quaternary phosphonium salt series and derivatives thereof. Described nonionic surfactant refers to organic acid ester, polyoxyethylene sorbitan monooleate, sorbitan fatty acid ester. The cationic-nonionic amphoteric surfactant and the anionic-nonionic amphoteric surfactant refer to the combination of the amphoteric surfactant and a single type of amphoteric surfactant having both the amphoteric characteristics. The role of surfactants is different from the emulsification of catalysts. The fused-ring aromatics include benzene, naphthalene, phenanthrene, anthracene, quinoline, thiophene, and alkyl substitutions including the above-mentioned aromatics and their mixtures, as well as aromatics extraction oil, catalytic oil slurry, anthracene oil and coal tar one or more of them. The organic alcohol is one or more of normal or isomeric C ₁ -C ₂₂ monohydric alcohols, dihydric alcohols, trihydric alcohols, and tetrahydric alcohols. The organic carboxylic acid is one or more of normal or isomeric C ₁ -C ₂₂ monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids, and also includes various cyclic One or more of alkanoic acid and various aromatic acids, and a mixture of the above-mentioned carboxylic acids; the organic carboxylate is one of the monovalent salts, divalent salts, and trivalent salts of the above-mentioned organic carboxylic acids or several, that is, one or more of alkali metals, alkaline earth metals, aluminum group metals, and all subgroup elements; the organic carboxylic acid amide is one or more of the amides of the above-mentioned organic carboxylic acids; The organic carboxylic acid halide is one or more of the above-mentioned organic carboxylic acid halides. The organic phosphorus compound is triphenyl phosphate, triphenylphosphine, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, trinaphthyl phosphate and other types of phosphate triester one or more of. The use temperature of the hydrogenation catalyst is less than 900°C.

Example 1

Table 1 Properties of feedstock for suspension bed hydrogenation project raw material one raw material two

Density (20C)/g·cm ^-3 0.9442 1.0085 Viscosity (100C)/mm ² ·s ^-1 108.7 744.2 Elemental composition C/m% 86.6 86.08 H/m% 12.5 11.13 N/m% 0.41 0.60 S/m% 0.13 2.27 V,PPm 1.8 333.4 Ni,PPm 81 55.7 Ca/μg/g 346 47.3   carbon residue/m% 7.0 18.66 Four components Saturated part (m%) 50.4 28.10 Aromatic content (m%) 22.2 37.63 Colloid (m%) 27.2 17.39   Asphaltenes (m%) 0.2 16.88

Table 2 batch reaction device The present invention is suitable for raw material-application example blank Example two Example three Raw material type raw material one raw material one raw material one Reaction temperature, °C 440 440 440 Reaction pressure, Mpa 7.0 7.0 7.0 Main catalyst concentration, μg/g constant constant constant Additive dosage, μg/g 0 500 750 Operating time, hours 1 1 1 Raw material handling capacity, g 200 200 200 Yield (m%) <180°C light oil+gas 23.3 22.6 21.5 180～360℃ Diesel 31.7 30.0 30.5 360～524℃ wax oil 28.5 30.6 31.4 ＞524℃ residue oil 14.5 15.0 14.8 Reactant liquid coke content 2.0 1.8 1.8 Amount of coke in the reactor, g 3.356 0.610 0.331 Reactor coking reduction rate -- 82% 91%

Example 2

Table 3 Batch type reaction device The present invention is applicable to the second application example of raw material blank Example two Example three Raw material type raw material two raw material two raw material two Reaction temperature, °C 435 435 435 Reaction pressure, Mpa 7.0 7.0 7.0 Main catalyst concentration, μg/g constant constant constant Additive dosage, μg/g 0 500 750 Operating time, hours 1 1 1 Raw material handling capacity, g 200 200 200 Yield (m%) <180°C light oil+gas 15.7 14.2 13.0 180～360℃ Diesel 22.0 22.0 21.5 360～524℃ wax oil 25.5 26.6 28.4 ＞524℃ residue oil 34.5 34.5 34.5 Reactant liquid coke content 3.3 2.7 2.6 Amount of coke in the reactor, g 7.3730 4.6237 1.9957 Reactor coking reduction rate -- 38% 73%

Example 3

Table 4 continuous reaction device The present invention is applicable to raw material-application example blank Example two Example three Raw material type raw material one raw material one raw material one Reaction temperature, °C 450 450 450 Reaction pressure, Mpa 11.0 11.0 11.0 Airspeed, H ^-1 1.0 1.0 1.0 hydrogen oil ratio, 800 800 800 Additive dosage, μg/g 0 500 750

main catalyst constant constant constant Running time, days 10 10 10   Raw material handling capacity, Kg 200 200 200 Yield (m%) gas 4.5 3.4 3.3  ＜180℃ light oil 15.6 11.6 11.6 180～360℃ Diesel 34.8 33.8 33.7 360～524℃ wax oil 29.0 34.5 34.8 ＞524℃ residual oil 16.1 16.7 16.6   Reactant liquid coke content 1.50 1.35 1.30   Reactor coking amount, g 314.6 40.6 30.0   Reduction rate of reactor coking -- 87.1% 90.5%

As can be seen from the above examples, under the same conditions, after applying the catalyst additive provided by the present invention, the amount of coking on the reactor is significantly reduced, and the greater the amount of additive added, the higher the reduction rate of the amount of coking in the reactor . This is because the present invention is developed for the hydrogenation process of the suspended bed of residual oil. Under the various effects of catalyst promoter components, a protective film can be formed on the surface of the reactor to reduce the coking of the reactor at high temperature, and at the same time It helps to improve the coke suppression effect of the catalyst in hydrogenation, and reduces the coking and fouling of the residual oil and reaction products in the heating furnace tube, reaction tube transportation and fractionation.

Claims (8)

1. A residual oil suspended bed hydrogenation aid, characterized in that it contains any one or any two or any combination of two or more of the following substances: natural organic polymers, synthetic organic polymers, natural surfactants , synthetic surfactants, condensed ring aromatics, organic alcohols, organic carboxylic acids, organic carboxylates, organic carboxylic acid amides, organic carboxylic acid halides and organic phosphides, the addition amount of which is 10-8000 μg/g of the residual oil raw material . 2. According to claim 1, the hydrogenation aid for residual oil suspended bed is characterized in that said auxiliary agent is applied to the hydrogenation process of residual oil suspended bed, or applied to residual oil and coal or residual oil and waste plastics or Residual oil and waste rubber or waste plastic and waste rubber hydrogenation co-smelting process or suspension bed hydrogenation process of coal liquefaction. 3. according to claim 1 described residue suspension bed hydrogenation aid, it is characterized in that said natural organic macromolecule or synthetic organic macromolecule is natural starch or cellulose or polyethylene glycol or p-phenylene Dicarboxylic acid ethylene glycol polycondensate, or terephthalic acid ethylenediamine polycondensate, or other dibasic carboxylic acid ethylene glycol polycondensate, or other dibasic carboxylic acid diamine polycondensate, including the above-mentioned natural or Modified products of synthetic polymers, polyacrylamide, polyacrylonitrile, partially hydrolyzed polyacrylamide, phenolic resin and their derivatives, also including polyethylene, or polypropylene, or polystyrene and their modified products and Derivatives; the molecular weight range of the natural organic macromolecule or synthetic organic macromolecule is 100-20,000,000. 4. according to the described hydrogenation aid of residual oil suspended bed of claim 1, it is characterized in that said surfactant comprises anionic surfactant, cationic surfactant, nonionic surfactant, cationic-nonionic surfactant Amphoteric surfactants, anionic-nonionic amphoteric surfactants; the so-called anionic surfactants refer to alkylbenzenesulfonic acid series, alkylbenzenesulfonate series, alkylnaphthalenesulfonic acid series, alkylnaphthalenesulfonate series, organic sulfate series, organic phosphate series, organic fatty acid series, sulfonated lignite and sulfonated pitch and their derivatives, petroleum sulfonate, lignin sulfonate; the cationic surfactants mentioned include organic quaternary ammonium Salt series, organic quaternary phosphonium salt series and their derivatives; said nonionic surfactants refer to organic acid esters, polyoxyethylene sorbitan monooleate, sorbitan fatty acid esters; said cationic— Nonionic amphoteric surfactants and anionic-nonionic amphoteric surfactants refer to the compounding of said amphoteric surfactants and a single type of amphoteric surfactants having both said amphoteric characteristics. 5. according to the described residual oil suspension bed hydrogenation aid of claim 1, it is characterized in that said condensed ring aromatic hydrocarbon comprises benzene, naphthalene, phenanthrene, anthracene, quinoline, thiophene and the alkyl substitution that comprises above-mentioned aromatic hydrocarbon substances and their mixtures, and also include one or more of aromatics extraction oil, catalytic oil slurry, anthracene oil and coal tar. 6. according to claim 1 described residue suspension bed hydrogenation aid, it is characterized in that said organic alcohol is normal C ₁ -C ₂₂ monohydric alcohol, dibasic alcohol, tribasic alcohol, tetrahydric alcohol One or more of them, or one or more of isomeric C ₁ -C ₂₂ monohydric alcohols, dihydric alcohols, trihydric alcohols, and tetrahydric alcohols. 7. according to the described hydrogenation aid of residual oil suspension bed of claim 1, it is characterized in that said organic carboxylic acid is normal C ₁ -C ₂₂ monocarboxylic acid, dicarboxylic acid, tricarboxylic acid , one or more of tetracarboxylic acids, or one or more of isomeric C ₁ -C ₂₂ monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids, It also includes one or more of various naphthenic acids and various aromatic acids, and a mixture of the above-mentioned carboxylic acids, and also includes one or more of various naphthenic acids and various aromatic acids, and the above-mentioned carboxylic acids A mixture of acids; said organic carboxylate is one or more of the above-mentioned monovalent salts, divalent salts and trivalent salts of organic carboxylic acids, that is, alkali metals, alkaline earth metals, aluminum group metals and all secondary One or more of the group elements; said organic carboxylic acid amide is one or more of the amides of the above-mentioned organic carboxylic acids; said organic carboxylic acid halides are the one or several. 8. according to the described hydrogenation aid of residual oil suspended bed of claim 1, it is characterized in that described organophosphorus compound is triphenyl phosphate, triphenyl phosphorus, trimethyl phosphate, triethyl phosphate, triphenyl phosphate One or more of propyl ester, tributyl phosphate, trinaphthyl phosphate and other types of phosphate triester.