A production method and production system of white oil for animal vaccines

Abstract

The application discloses a production method and a production system of white oil for animal vaccines, and the production method is characterized in that: firstly, raw materials are cut and separated to obtain light components and heavy components; the heavy components enter an adsorption-isomerization reaction unit to be in contact with a catalyst, and after treatment, a material flow A is obtained; when the refractive index of the material flow A is higher than that of the heavy components, the heavy components stop entering the adsorption-isomerization reaction unit; hydrogen is introduced into the adsorption-isomerization reaction unit to generate an isomerization condensation reaction, and the reaction product is further subjected to a hydrogenation refining reaction; after the reaction effluent is separated, a gas phase product, light white oil and white oil for animal vaccines are obtained. According to the method, non-ideal components are separated in advance, so that the isomerization condensation reaction is only performed on raw materials rich in ideal components, hydrogenation refining and isomerization condensation processing loads are reduced, hydrogen consumption in the process is reduced, and the economic efficiency of the device is improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of petrochemical industry, and particularly relates to a production method of white oil for animal vaccine. BACKGROUND

[0002] In recent years, with the improvement of people's living standards and the increase of policy support, China's animal husbandry has gradually developed towards industrialization, large-scale and standardization, and the product quality and economic benefits have been continuously improved. Under this environment, the animal vaccine industry has also risen. On the one hand, large-scale breeding has high requirements for animal epidemic prevention. On the other hand, people gradually pay attention to the field of food safety and realize that animal epidemic prevention is the most effective means to control the spread of infectious diseases. As of 2018, the market size of animal vaccines in China has reached nearly 20 billion yuan, and is expected to reach 26.9 billion yuan in 2024. At present, the global animal vaccine market is mainly controlled by developed countries, and European and American countries account for more than 80% of the market share.

[0003] In view of the broad market prospects of domestic animal vaccines, the potential can be tapped, and the independent research and development and production of high-end white oil for animal vaccines have great significance. At present, the demand for white oil for animal vaccines is about 15,000 tons / year, and its quality standard is formulated by the China Veterinary Drug Committee. The injection white oil has strict restrictions on the content of condensed ring aromatics, heavy metals and toxic metals.

[0004] At present, the overall crude oil in the world is showing a trend of deterioration, and the content of non-ideal components such as sulfur, nitrogen, condensed ring aromatics and metals is increasing, which makes the raw materials suitable for producing white oil for animal vaccines gradually decrease. The energy consumption of producing white oil for animal vaccines by hydrogenation of inferior raw materials is high, and the process is complex. On the other hand, China is facing a serious problem of diesel production overcapacity, and realizing diesel de-capacity and industrial structure transformation is a major problem that needs to be solved. Among them, "oil to special" is an effective solution, which uses excess diesel to produce high-value white oil for animal vaccines, which can effectively solve the problem of diesel production overcapacity and maximize benefits.

[0005] CN 101475837 discloses a method for preparing low-aromatic low-viscosity narrow-cut injection white oil: (1) distilling relevant petroleum products to obtain a 270℃-320℃ fraction as injection white oil raw material; (2) removing sulfur, nitrogen, olefins, gum, heavy metals and most of the aromatic impurities in the raw material by first-stage hydrogenation reaction; (3) obtaining de-aromatic white oil with an aromatic content of <50 ppm by second-stage hydrogenation reaction; (4) using 13X molecular sieve to adsorb and refine the de-aromatic white oil to remove its odor and mechanical impurities, and obtaining refined injection white oil.

[0006] CN 112625743A discloses a high-quality medicinal white oil and its preparation process: (1) remove sulfur, nitrogen, oxygen and other heteroatoms in the raw oil by hydrogenation pre-refining to avoid poisoning of the second-stage noble metal catalyst, and at the same time, a part of the aromatic hydrocarbons is hydrogenated and saturated; (2) hydrogenate and saturate the aromatic hydrocarbons in the pre-refined oil to produce medicinal white oil.

[0007] CN 111334330A discloses a white oil for poultry vaccine injection and a preparation method thereof: (1) mixing the atmospheric and vacuum distillate oil of paraffin-based raw oil and the atmospheric and vacuum distillate oil of naphthenic-based raw oil to obtain a mixed distillate; (2) hydrogenation pre-refining the mixed distillate, and sequentially implementing hydrogenation treatment, isomerization and condensation reduction, and hydrogenation supplemental refining on the hydrogenation pre-refined product under a hydrogen partial pressure of 15.0-20.0 MPa; (3) distilling out the 290℃-370℃ fraction of the supplemental refined product to obtain the white oil for poultry vaccine injection.

[0008] CN 113278444A discloses a production method of a white oil adjuvant for veterinary vaccines: (1) heating mineral oil as raw material and adding it into a first reactor to react with hydrogenation desulfurization catalyst I to obtain reaction product A; (2) adding reaction product A into a second reactor to react with hydrogenation de-aromatic catalyst II to carry out hydrogenation de-aromatic and hydrogenation saturation reactions to obtain reaction product B; (3) adding reaction product B into a third reactor to carry out hydrogenation isomerization reaction with hydrogenation isomerization catalyst III; (4) cooling reaction product C and adding it into a fourth reactor to react with hydrogenation saturation refining catalyst IV to carry out hydrogenation supplemental refining and remove unsaturated hydrocarbons in reaction product C to obtain reaction product D; (5) cutting reaction product D to obtain white oil adjuvants for veterinary vaccines with different viscosities. SUMMARY

[0009] Currently, the hydrogenation production of traditional white oil for animal vaccines mostly uses atmospheric and vacuum distillate oil as raw material, which has high content of sulfur, nitrogen, metals, aromatic hydrocarbons and polycyclic naphthenes, and adopts two-stage or more hydrogenation treatment, which has problems such as high processing difficulty, high hydrogen consumption and energy consumption, high investment, complex process, etc. The applicant proposes that if diesel oil (hydrocracking diesel oil, hydrotreated diesel oil or hydrorefined diesel oil) is used as the raw material for animal vaccine white oil, most of the non-ideal components such as aromatic hydrocarbons and polycyclic naphthenes contained therein are selectively adsorbed and removed, and isomerization and condensation reduction treatment is not performed, on the one hand, it can greatly reduce the production difficulty of the product and improve the product quality, on the other hand, it can greatly reduce the hydrogen consumption, device operation and production cost of the isomerization and condensation reduction process, and at the same time, realize the production of diesel oil, product structure upgrading of the refinery and maximization of economic benefits.

[0010] In view of the above problems and deficiencies in the prior art, the main purpose of the present application is to provide a production method and system of white oil for animal vaccine, in which most of the non-ideal components such as aromatic hydrocarbons and polycyclic naphthenes in the diesel raw material after pre-separation treatment are separated out through a selective adsorption process, and then the adsorption-treated raw material only containing normal alkanes, long-chain isomeric alkanes and long-side-chain monocyclic naphthenes is subjected to isomerization and deep hydrofining to produce white oil for animal vaccine.

[0011] To achieve the above-mentioned purpose, the present application provides a production method of white oil for animal vaccine, comprising the following steps:

[0012] (1) separating the diesel raw material under cutting conditions to obtain light components and heavy components;

[0013] (2) introducing the heavy components into an adsorption-isomerization reaction unit to contact with the catalyst packed in the adsorption-isomerization reaction unit, and obtaining a stream A after treatment, which is recycled back to the adsorption-isomerization reaction unit for treatment;

[0014] (3) when the refractive index (20℃) of the stream A is 0.1% to 5% higher than that of the heavy components, stopping the heavy components from entering the adsorption-isomerization reaction unit;

[0015] (4) introducing hydrogen into the adsorption-isomerization reaction unit to make the adsorbate undergo isomerization and condensation reaction under the action of the catalyst and hydrogen, and obtaining a stream B after treatment;

[0016] (5) introducing the stream B and the light components into a hydrofining reaction unit to perform hydrofining reaction under the action of hydrogen and hydrofining catalyst, and obtaining gaseous products, light white oil and white oil for animal vaccine after separation of the reaction effluent.

[0017] Further, in the above-mentioned production method of white oil for animal vaccine, the diesel raw material can be selected from at least one of hydrocracking diesel, hydrotreated diesel and hydrorefined diesel.

[0018] Further, in the above-mentioned production method of white oil for animal vaccine, the diesel raw material has a paraffin content of not less than 45wt%, an aromatic hydrocarbon content of not higher than 10wt%, a condensation point of not higher than 5℃, a nitrogen content of not higher than 2 ppm and a sulfur content of not higher than 10 ppm.

[0019] Further, in the above-mentioned production method of white oil for animal vaccine, the cutting point temperature of the light components and the heavy components in step (1) is 260 to 280℃.

[0020] Further, in the above method for producing white oil for animal vaccine, at least one reactor is arranged in the adsorption-isomerization reaction unit, preferably two reactors are arranged, and the two reactors are connected in parallel and switched to use, when one of the reactors completes the adsorption reaction and introduces hydrogen for isomerization and condensation reaction, the recombined components are switched to the other reactor for adsorption reaction; the reactor can use one or several of the existing fixed bed reactor, fluidized bed reactor, slurry bed reactor, preferably a fixed bed reactor.

[0021] Further, in the above method for producing white oil for animal vaccine, in step (2), the operating conditions of the adsorption reaction in the adsorption-isomerization reaction unit are as follows: the temperature is 40-250°C, preferably 60-200°C, the pressure is 0.01-0.5 MPa, preferably 0.08-0.1 MPa, the volume space velocity is 0.05-5.0 h -1 -1 , preferably 0.1-2.0 h -1 -1 .

[0022] Further, in the above method for producing white oil for animal vaccine, in step (3), when the refractive index (20°C) of the stream A is 0.5-2.5% higher than the refractive index (20°C) of the recombined components, the recombined components stop entering the adsorption-isomerization reaction unit.

[0023] Further, in the above method for producing white oil for animal vaccine, in step (4), the operating conditions of the isomerization and condensation reaction in the adsorption-isomerization reaction unit are as follows: the reaction temperature is 200-420°C, preferably 270-380°C, the hydrogen partial pressure is 1.0-20.0 MPa, preferably 3.0-15.0 MPa, the volume space velocity is 0.1-10.0 h -1 , preferably 0.5-3.0 h -1 , the hydrogen-oil volume ratio is 100:1-1500:1, preferably 100:1-400:1.

[0024] Further, in the above method for producing white oil for animal vaccine, in step (5), the separation generally includes gas-liquid separation and fractionation, the hydrogenation refined reaction product first enters the gas-liquid separation zone for gas-liquid separation, and after separation, a gas phase stream and a liquid phase stream are obtained, the gas phase stream can be purified and used as circulating hydrogen to circulate back to the adsorption-isomerization reaction unit and the hydrogenation refined reaction unit; the liquid phase stream enters the fractionation column for separation, and according to actual needs, light white oil and white oil for animal vaccine can be obtained after separation. The gas-liquid separation zone can use any one of the existing devices that can realize gas-liquid two-phase separation function in the field, such as a gas-liquid separator, a flash column, etc.

[0025] ​​Further, in the above method for producing white oil for animal vaccines, the catalyst comprises an intergrowth of a TON structure molecular sieve and a 5A molecular sieve, an active metal component, and an inorganic refractory oxide; preferably, the TON structure molecular sieve is intergrown on at least a part of the surface of the 5A molecular sieve at a predetermined surface coverage, and the suitable surface coverage can be 0.5% or more or 1% or more, and 50% or less or 20% or less, but the present application is not limited thereto.

[0026] According to one embodiment of the present application, the intergrowth molecular sieve has a specific surface area of 300 m 2 / g to 600 m 2 / g, and a pore volume of 0.15 cm 3 / g to 0.40 cm 3 / g.

[0027] According to one embodiment of the present application, the catalyst has a specific surface area of 200 m 2 / g to 550 m 2 / g, and a pore volume of 0.25 cm 3 / g to 0.60 cm 3 / g.

[0028] According to one embodiment of the present application, the weight ratio of the 5A molecular sieve to the TON structure molecular sieve is 1:80 to 3:1, preferably 1:30 to 1:1.

[0029] According to one embodiment of the present application, the content of the TON structure molecular sieve is 10 wt% to 80 wt%, preferably 20 wt% to 60 wt%, and the content of the 5A molecular sieve is 1 wt% to 50 wt%, preferably 2 wt% to 20 wt%, relative to the total weight of the catalyst being 100 wt%.

[0030] According to one embodiment of the present application, the content of the intergrowth molecular sieve is 10 wt% to 90 wt%, preferably 20 wt% to 70 wt%, and the content of the active metal component in terms of metal elements is 0.05 wt% to 5.0 wt%, preferably 0.1 wt% to 1.0 wt%, relative to the total weight of the catalyst being 100 wt%.

[0031] According to one embodiment of the present application, the inorganic refractory oxide is selected from one or more of alumina, titania, boria, silica, zirconia, and magnesia, preferably alumina.

[0032] According to one embodiment of the present application, the active metal component is selected from at least one of the Group VIII noble metals of the periodic table, preferably at least one of Pt and Pd, in particular Pt.

[0033] According to one embodiment of the present application, the TON structure molecular sieve is selected from one or more of ZSM-22, Theta-1, ISI-1, KZ-2 and NU-10, preferably ZSM-22.

[0034] According to one embodiment of the present application, the 5A type molecular sieve is selected from 5A molecular sieve.

[0035] According to one embodiment of the present application, the catalyst is prepared by kneading the mosaic molecular sieve with inorganic refractory oxide, extrusion aid, binder, further forming a carrier by extruding into strips, and then loading active metal to obtain the catalyst.

[0036] According to one embodiment of the present application, the extrusion aid and binder can use the reagents commonly used in the art, and the general extrusion aid can be pearl millet powder, and the binder can be aqueous solution of inorganic acid, such as nitric acid.

[0037] According to one embodiment of the present application, the preparation method of the mosaic molecular sieve comprises the following steps:

[0038] (1) contacting a silicon source, an aluminum source and an alkali source in the presence of a template agent, a TON structure molecular sieve and water to obtain a gel mixture, and

[0039] (2) hydrothermally crystallizing the gel mixture, and then washing, drying and calcining to obtain a first mosaic molecular sieve.

[0040] According to one embodiment of the present application, the preparation method further comprises the following step:

[0041] (3) calcium exchanging the first mosaic molecular sieve, and then washing, drying and calcining to obtain a second mosaic molecular sieve.

[0042] According to one embodiment of the present application, in step (1), the silicon source is selected from at least one of water glass, sodium silicate, methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate.

[0043] According to one embodiment of the present application, in step (1), the alkali source is selected from at least one of alkali metal hydroxide, preferably sodium hydroxide.

[0044] According to one embodiment of the present application, in step (1), the aluminum source is selected from at least one of sodium metaaluminate, aluminum isopropoxide, aluminum sulfate, aluminum hydroxide, aluminum oxide and pseudo-boehmite.

[0045] According to one embodiment of the present application, in step (1), the template agent is selected from at least one of polyethylene oxide triblock copolymer (P123), dimethyloctadecyl [3- (trimethoxysilyl) propyl] ammonium chloride (TPOAC).

[0046] According to one embodiment of the present application, in step (1), the TON structure molecular sieve is selected from one or more of ZSM-22, Theta-1, ISI-1, KZ-2 and NU-10, preferably ZSM-22.

[0047] According to one embodiment of the present application, in step (1), the operation condition of the contacting includes: temperature of 15-30℃, time of 1-4h under the presence of stirring.

[0048] According to one embodiment of the present application, in step (1), the molar ratio of the alkali source (calculated as oxide), the silicon source (calculated as SiO2), the aluminum source (calculated as Al2O3), the template agent and water is (0.5-2.5):1:(0.4-0.7):(0.001-0.08):(30-200), and the amount of the TON structure molecular sieve is 0.3-8 times, preferably 1-7 times of the amount of the silicon source.

[0049] According to one embodiment of the present application, in step (2), the hydrothermal crystallization temperature is 60-120℃, and the crystallization time is 2-16h.

[0050] According to one embodiment of the present application, in step (2), the drying temperature is 80-200℃, and the drying time is 2-24h.

[0051] According to one embodiment of the present application, in step (2), the calcination temperature is 400-600℃, and the calcination time is 2-12h.

[0052] According to one embodiment of the present application, in step (3), the operation condition of the calcium exchange includes: exchange temperature of 60-100℃, exchange time of 1-12h, and calcium ion concentration in the calcium exchange solution of 0.1-2.5mol / L.

[0053] According to one embodiment of the present application, in step (3), the drying temperature is 80-150℃, and the drying time is 2-12h.

[0054] According to one embodiment of the present application, in step (3), the calcination temperature is 300-500℃, and the calcination time is 2-8h.

[0055] Further, in the production method of the white oil for animal vaccine, the hydrofining catalyst used in the hydrofining reaction unit can be selected from commercially available products or prepared according to the methods disclosed in the art. Specifically, it can be one or more of sulfided hydrofining agent, bulk hydrofining agent, reduced Ni-based catalyst, noble metal hydrofining agent, and preferably reduced Ni-based catalyst or noble metal hydrofining agent. For example, it can be FTX-3, FF-36 / 66, FHDS-2 / 3, FMTA-2 / 20, FHJ-2 hydrofining catalyst developed by SINOPEC (Dalian) Petroleum Chemical Research Institute Co., Ltd.

[0056] Further, in the production method of the white oil for animal vaccine, the hydrofining operation conditions of the hydrofining reaction unit in step (5) are as follows: the reaction temperature is 200-350°C, preferably 200-260°C; the hydrogen partial pressure is 1.0-20.0 MPa, preferably 4.5-15.0 MPa; the volume space velocity is 0.1-10.0 h -1 , preferably 0.5-1.0 h -1 ; and the hydrogen / oil volume ratio is 100:1-1500:1, preferably 200:1-800:1.

[0057] Further, in the production method of the white oil for animal vaccine, the hydrofining reaction unit can be provided with one or more reactors, which can be one or more of existing fixed bed hydrogenation reactor, fluidized bed hydrogenation reactor, and slurry bed hydrogenation reactor, and preferably a fixed bed hydrogenation reactor.

[0058] Further, in the production method of the white oil for animal vaccine, the adsorption-isomerization reaction unit and the hydrofining reaction unit are connected in series.

[0059] The second aspect of the present application provides a production system of white oil for animal vaccine, comprising:

[0060] a fractionation unit for receiving diesel raw material and separating it, so as to obtain light components and heavy components;

[0061] an adsorption-isomerization reaction unit for receiving the heavy components from the fractionation unit, and contacting the heavy components with the catalyst loaded in the adsorption-isomerization reaction unit for adsorption treatment, so as to obtain a stream A returned to the adsorption-isomerization reaction unit for recycling treatment; when the refractive index (20°C) of the stream A is 0.1-5% higher than the refractive index (20°C) of the heavy components, the heavy components stop entering the adsorption-isomerization reaction unit, and hydrogen is introduced into the adsorption-isomerization reaction unit, so as to occur isomerization and condensation reaction under the action of the catalyst and hydrogen, and a stream B is obtained after treatment;

[0062] a hydrofining reaction unit for receiving hydrogen, stream B from the adsorption-isomerization reaction unit and light components from the fractionation unit, the hydrofining reaction unit being packed with a hydrofining catalyst, and the stream B and the light components being subjected to a hydrofining reaction in the presence of the hydrofining catalyst and the hydrogen;

[0063] a gas-liquid separation zone for receiving the hydrofining reaction effluent from the hydrofining reaction unit, and separating the hydrofining reaction effluent into a gas phase stream and a liquid phase stream;

[0064] a fractionation column for receiving the liquid phase stream from the gas-liquid separation zone, and separating the liquid phase stream into light white oil and white oil for animal vaccine.

[0065] Further, in the production system of the white oil for animal vaccine, the adsorption-isomerization reaction unit is provided with at least one reactor, preferably two reactors, and the two reactors are connected in parallel and used alternately, when one reactor completes the adsorption reaction and introduces hydrogen for isomerization reaction, the heavy components are switched to the other reactor for adsorption reaction; the reactor can be one or several of the existing fixed bed reactor, fluidized bed reactor, slurry bed reactor, and preferably a fixed bed reactor.

[0066] Further, in the production system of the white oil for animal vaccine, the hydrofining reaction unit can be provided with more than one reactor, and the reactor can be one or several of the existing fixed bed hydrogenation reactor, fluidized bed hydrogenation reactor, slurry bed hydrogenation reactor, and preferably a fixed bed hydrogenation reactor.

[0067] Further, in the production system of the white oil for animal vaccine, the adsorption-isomerization reaction unit and the hydrofining reaction unit are connected in series.

[0068] Further, in the production system of the white oil for animal vaccine, the gas-liquid separation zone can use any of the existing devices that can realize the function of gas-liquid two-phase separation in the art, such as a gas-liquid separator, a flash column, etc.

[0069] Further, in the production system of the white oil for animal vaccine, the gas phase stream separated by the gas-liquid separation zone is subjected to purification treatment and then communicated with the adsorption-isomerization reaction unit and / or the hydrofining reaction unit through a pipeline, and used as circulating hydrogen.

[0070] Compared with the prior art, the production method and production system of the white oil for animal vaccine provided by the present application have the following advantages:

[0071] 1. The animal vaccine white oil production method provided by the present application uses diesel oil, such as hydrocracking diesel oil, hydrotreated diesel oil or hydrorefined diesel oil, as raw material, and utilizes the advantages of low sulfur, nitrogen, metal and aromatic hydrocarbon content, etc. By pre-adsorbing the diesel oil raw material, part of the non-ideal components such as polycyclic naphthenes and aromatic hydrocarbons are separated out, so that only the ideal components such as long-chain isomeric alkanes, long-side-chain monocyclic naphthenes and long-chain monocyclic aromatic hydrocarbons are subjected to isomerization and condensation reduction reaction, which greatly reduces the refining difficulty, the participation of non-ideal components in hydrogenation reaction, i.e. reduces the hydrogenation refining and isomerization condensation reduction processing load, and reduces the hydrogen consumption of the process, and improves the economic efficiency of the device. At the same time, the above-mentioned "oil conversion" process can realize the de-energization of diesel oil, the upgrading of refinery product structure and the maximization of economic benefits. Moreover, the applicant found in the research process that the addition of 5A molecular sieve in the currently used hydroisomerization dewaxing catalyst has selective adsorption effect on the raw material of lubricating oil base oil in the absence of hydrogen, which can separate out the non-ideal components such as two-ring or more ring naphthenes with low viscosity index and part of aromatic hydrocarbons from the raw material, thereby reducing the content of non-ideal components from the raw material.

[0072] 2. In the animal vaccine white oil production method provided by the present application, the catalyst has the selective adsorption ability to long-chain isomeric alkanes, long-side-chain monocyclic naphthenes and long-chain monocyclic aromatic hydrocarbons, and the ability to selectively isomerize alkanes in the presence of hydrogen and under suitable reaction conditions, which simplifies the production process of the animal vaccine white oil, reduces the device investment and reduces the hydrogen consumption of the process.

[0073] 3. In the animal vaccine white oil production method provided by the present application, in addition to producing animal vaccine white oil, diesel oil light components and part of cracking light components can also be used to produce light white oil, so as to make full use of the raw materials and achieve efficient utilization. BRIEF DESCRIPTION OF DRAWINGS

[0074] Figure 1 The figure is a flowchart of the animal vaccine white oil production method of the first embodiment of the present application.

[0075] Figure 2 The figure is a flowchart of the animal vaccine white oil production method of the second embodiment of the present application. DETAILED DESCRIPTION

[0076] The present application will be further described in conjunction with the drawings and specific embodiments. The following examples will further illustrate the method provided by the present application, but do not limit the scope of the present application.

[0077] Unless otherwise explicitly stated, throughout the specification and claims, the term "comprise" or its variants such as "comprises" or "comprising" will be understood to encompass the stated element or elements or components, and not to preclude other elements or components.

[0078] In this document, spatially relative terms, such as "beneath", "below", "lower", "above", "upper", and the like, can be used to describe an element's or feature's relationship to another element or feature as illustrated in the figures. The spatially relative terms are intended to encompass different orientations of the object in use or operation in addition to the orientations depicted in the figures. For example, if an object in the figures is turned over, elements described as "below" or "beneath" other elements or features would then be oriented "above" the other elements or features. Thus, the exemplary term "below" can encompass both an orientation of above and below. The object can be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative terms used herein interpreted accordingly.

[0079] In this document, the terms "first", "second", etc. are used to distinguish between two different elements or portions, and are not used to define a particular position or relative relationship. In other words, the terms "first", "second", etc. can also be interchanged with each other in some embodiments.

[0080] In this document, all numerical values of parameters (e.g., quantities or conditions) should be understood to be modified in all instances by the term "about", whether or not the term "about" actually appears before the numerical value.

[0081] In the context of the present specification, unless explicitly stated otherwise, both the silicon-aluminum material and the catalyst are subjected to a calcination treatment before measurement, sometimes referred to as "calcined form". Here, the conditions of the calcination treatment include a calcination temperature of 600°C in an air atmosphere and a calcination time of 3 hours or more.

[0082] In the context of the present specification, long-side-chain hydrocarbons particularly refer to one or more of long-side-chain isomeric alkanes, long-side-chain monocyclic naphthenes, and long-side-chain monocyclic aromatics, excluding other hydrocarbons with long-side-chains. In addition, according to the present invention, the so-called long-side-chain refers to a C8-22 (preferably C10-18) straight-chain alkyl group as a side chain.

[0083] In the context of the present specification, a mechanical mixture refers to a mixture of two or more materials obtained by mechanical mixing. Here, the mechanical mixing includes simple mixing, grinding, pulping, and the like.

[0084] In the context of the present specification, an inlaid molecular sieve refers to a composite crystal having two or more molecular sieve structural characteristics, in which the surface or the interior of one or more molecular sieve crystals is inlaid with another one or more molecular sieves. In contrast to a mechanical mixture, the different molecular sieves are more tightly bound in the inlaid structure, truly forming an integrated composite structure at the molecular level.

[0085] In the context of the present specification, the refractive index is represented by a Mettler refractometer R5, the long-chain hydrocarbon content is represented by an Agilent gas chromatograph 7890, the XRD pattern of the sample is represented by a D / max-2500 full-automatic rotating target X-ray diffractometer, the specific surface area, pore volume and average pore diameter of the mosaic molecular sieve and the specific surface area, pore volume and average pore diameter of the catalyst are represented by an ASAP 2405 physical adsorption instrument by N2 adsorption-desorption method, and the calcium content of the calcium-type molecular sieve is represented by X-ray fluorescence diffraction.

[0086] In the context of the present specification, the TON structure molecular sieve content in the mosaic molecular sieve is quantitatively analyzed by XRD.

[0087] In the present specification, all percentages, parts, ratios, etc. mentioned are by weight, the pressure is gauge pressure, and the weight or content is on a dry basis, unless otherwise specified.

[0088] As shown in Figure 1 The present application provides a production method of white oil for animal vaccine. Diesel oil raw material 1 enters a fractionation unit 2 to be separated to obtain light components 3 and heavy components 4. The heavy components 4 enter an adsorption-isomerization reaction unit 5 to be treated by contacting with the catalyst filled in the adsorption-isomerization reaction unit 5. After treatment, a stream 7 is obtained, which is recycled back to the adsorption-isomerization reaction unit 5 for treatment. When the refractive index (20℃) of the stream 7 is 0.1% to 5% higher than that (20℃) of the heavy components 4, the introduction of the heavy components 4 into the adsorption-isomerization reaction unit 5 is stopped, and hydrogen 6 is introduced into the adsorption-isomerization reaction unit 5 to make the adsorbate undergo isomerization and condensation reaction under the action of the catalyst and hydrogen. After treatment, a stream 8 is obtained. The stream 8 and the light components enter a hydrofining reaction unit 9 to undergo hydrofining reaction under the action of hydrogen 6 and hydrofining catalyst. The hydrofining reaction effluent 10 enters a gas-liquid separation zone 11 to be separated to obtain a gas phase stream 12 and a liquid phase stream 13. The gas phase stream 12 can be purified and recycled as recycle hydrogen back to the adsorption-isomerization reaction unit 5 and / or the hydrofining reaction unit 9. The liquid phase stream 12 further enters a fractionation column 14 to be fractionated to obtain light white oil 16 and white oil for animal vaccine 15.

[0089] As shown in Figure 2As shown, the production method of white oil for animal vaccine provided by the present application is as follows: diesel oil raw material 1 enters a fractionation unit 2 to be separated to obtain light component 3 and heavy component 4, the heavy component 4 enters an adsorption-isomerization reaction unit (the adsorption-isomerization reaction unit includes reactors 5-1 and 5-2 arranged in parallel) and is treated by contacting with a catalyst filled in the reactor 5-1, to obtain a stream 7-1 after treatment, the stream 7-1 is recycled back to the reactor 5-1 for treatment; when the refractive index (20℃) of the stream 7-1 is 0.1% to 5% higher than the refractive index (20℃) of the heavy component 4, the heavy component 4 is switched from the reactor 5-1 to the reactor 5-2, and the above operation of the reactor 5-1 is repeated; hydrogen 6 is introduced into the reactor 5-1, so that the adsorbate is subjected to isomerization and condensation reaction under the action of the catalyst and the hydrogen, to obtain a stream 8 after treatment; when the refractive index (20℃) of the stream 7-2 of the reactor 5-2 is 0.1% to 5% higher than the refractive index (20℃) of the heavy component 4, the above operation of the reactor 5-1 is also repeated; the stream 8 and the light component 3 enter a hydrofining reaction unit 9 to be subjected to hydrofining reaction under the action of hydrogen 6 and a hydrofining catalyst, the hydrofining reaction effluent 10 enters a gas-liquid separation zone 11 to be separated to obtain a gas phase stream 12 and a liquid phase stream 13 after separation, the gas phase stream 12 can be subjected to purification treatment to be recycled back to the adsorption-isomerization reaction unit 5 and / or the hydrofining reaction unit 9 as circulating hydrogen; the liquid phase stream 12 further enters a fractionation tower 14 to be fractionated to obtain light white oil 16 and white oil for animal vaccine 15.

[0090] The raw material oil used in the method embodiment of the present application includes two kinds of hydrocracking diesel oil and hydrofining diesel oil, and the specific properties of the raw material oil are shown in Table 1. The hydrofining catalysts involved in Examples 1-4 and Comparative Examples 1-4 can be selected according to the properties of commercial catalysts, and in the method of the present application, the hydrofining catalyst can be selected from FMTA-20 catalyst, FMTA-2 catalyst, FTX-3 catalyst and the like.

[0091] Table 1 Properties of raw material oil

[0092]

[0093] Example 1

[0094] Put 128 g of sodium hydroxide, 208 g of ethyl orthosilicate, 82 g of sodium metaaluminate, 14.88 g of dimethyloctadecyl [3-(trimethoxysilyl) propyl] ammonium chloride (TPOAC) and 1800 g of water into a crystallization kettle, then add 300 g of ZSM-22 molecular sieve after stirring, seal the reaction kettle, heat to 110℃ and hydrothermally crystallize for 6 h. After crystallization is completed, the product obtained by crystallization is washed, then dried at 110℃ for 6 h, and then placed at 500℃ for calcination for 5 h, thereby obtaining the first eutectic molecular sieve Z1. Then the molecular sieve Z1 is ion exchanged in a 1.8 mol / L CaCl2 solution at 90℃ for 4 h, suction filtered and washed, then dried at 100℃ for 4 h, and then placed at 400℃ for calcination for 3 h, thereby obtaining the second eutectic molecular sieve GZ-1, which has a specific surface area of 452 m2 / g, a pore volume of 0.25 mL / g, and a TON type molecular sieve mass fraction of 85%.

[0095] Put 210 g of the above prepared eutectic molecular sieve GZ-1, 90 g of pseudo-boehmite (dry basis) and 20 g of sesbania powder into a mixing kettle, add 9 ml of concentrated nitric acid (65% by mass) and an appropriate amount of water, mix well, and then extrude into strips. The formed carrier is dried at 100℃ for 4 h and calcined at 550℃ for 4 h to obtain the carrier ES-1. Then the noble metal Pt is impregnated by using a saturated impregnation method, the Pt loading amount is 0.50 wt% of the carrier, dried at 100℃ for 6 h, and calcined at 500℃ for 3 h to obtain the catalyst numbered E-1.

[0096] Example 2

[0097] Put 64 g of sodium hydroxide, 208 g of ethyl orthosilicate, 98.4 g of sodium metaaluminate, 24.8 g of dimethyloctadecyl [3-(trimethoxysilyl) propyl] ammonium chloride (TPOAC) and 2700 g of water into a crystallization kettle, then add 240 g of ZSM-22 molecular sieve after stirring, seal the reaction kettle, heat to 100℃ and hydrothermally crystallize for 7 h. After crystallization is completed, the product obtained by crystallization is washed, then dried at 100℃ for 6 h, and then placed at 450℃ for calcination for 8 h, thereby obtaining the first eutectic molecular sieve Z2. Then the molecular sieve Z2 is ion exchanged in a 1.5 mol / L CaCl2 solution at 80℃ for 4 h, suction filtered and washed, then dried at 100℃ for 5 h, and then placed at 350℃ for calcination for 6 h, thereby obtaining the second eutectic molecular sieve GZ-2, which has a specific surface area of 498 m2 / g, a pore volume of 0.23 mL / g, and a TON type molecular sieve mass fraction of 82%.

[0098] The preparation process of the catalyst E-2 of the present application is the same as that of Example 1, except that the eutectic molecular sieve used is GZ-2 and the Pt loading amount is 0.48 wt% of the carrier, thereby obtaining the catalyst numbered E-2.

[0099] Examples 3-4

[0100] Examples 3-4, the raw material is two raw materials listed in Table 1 respectively, the adsorption-isomerization reaction unit uses catalyst E-1, the hydrofining reaction unit uses FMTA-20 catalyst, adopts the flow shown in the table, that is, the adsorption-isomerization reaction unit is a single reactor, and the results are shown in Table 2. Figure 1

[0101] Examples 5-6

[0102] Examples 5-6, the raw material is two raw materials listed in Table 1 respectively, the adsorption-isomerization reaction unit uses catalyst E-2, the hydrofining reaction unit uses FMTA-2 catalyst, adopts the flow shown in the table, that is, the adsorption-isomerization reaction unit is two reactors 5-1, 5-2 in parallel, and the results are shown in Table 3. Figure 2

[0103] Table 2 Process conditions and results of Examples 3-4

[0104]

[0105] Table 3 Process conditions and results of Examples 5-6

[0106]

[0107] Comparative Example 1

[0108] Take 134g of ZSM-22 molecular sieve (silicon aluminum ratio 90), 200g of 5A molecular sieve, 150g (aluminum oxide) of aluminum hydroxide (SB produced by Condean Company in Germany), 30g of sesbania powder, mix them evenly, then add water and concentrated nitric acid (mass concentration is 66.5wt%), fully knead, make it into a paste-like plastic, extrude into a cylindrical strip with a diameter of 1.5mm on the extruder, dry the cylindrical strip at 100℃ for 12 hours, then calcine at 550℃ in air atmosphere for 4 hours to obtain the catalyst carrier of the application.

[0109] Load 300g of the carrier with noble metal Pt by saturated impregnation method, then dry at 110℃ for 7 hours, calcine at 500℃ in air atmosphere for 3h, to obtain the catalyst of the application containing 0.49wt% Pt, numbered as C-D1.

[0110] Comparative Example 2

[0111] ​​A crystallization kettle was charged with 40 g of sodium hydroxide, 208 g of tetraethyl orthosilicate, 285.6 g of aluminum isopropoxide, 5.75 g of a polyethylene oxide triblock copolymer (P123), and 1440 g of water, and stirred to obtain a uniform mixture. Then, 60 g of Hβ molecular sieve was added, and the mixture was stirred. The kettle was sealed, heated to 90°C, and hydrothermally crystallized for 10 h. After crystallization, the product was washed, dried at 110°C for 6 h, and calcined at 450°C for 8 h to obtain a first inlaid molecular sieve. Then, the molecular sieve was ion-exchanged in a 1.8 mol / L CaCl2 solution at 90°C for 4 h, filtered, washed, dried at 100°C for 4 h, and calcined at 400°C for 3 h to obtain a second inlaid molecular sieve D.

[0112] The preparation process of the comparative catalyst C-D2 of the present application was the same as in Example 1, except that the inlaid molecular sieve D was used, and the Pt loading was 0.30 wt% of the carrier. The prepared catalyst was numbered C-D2.

[0113] Comparative Example 3

[0114] Comparative Example 3 used raw material 1 listed in Table 1, the adsorption-isomerization reaction unit used catalyst C-D1, the hydrofining reaction unit used FMTA-20 catalyst, and the process shown in Figure 1 was used, i.e., the adsorption-isomerization reaction unit was a single reactor, and the results are shown in Table 4.

[0115] Comparative Example 4

[0116] Comparative Example 4 used raw material 2 listed in Table 1, the adsorption-isomerization reaction unit used catalyst C-D2, the hydrofining reaction unit used FMTA-2 catalyst, and the process shown in Figure 2 was used, i.e., the adsorption-isomerization reaction unit was two reactors, and the results are shown in Table 4.

[0117] Table 4 Process conditions and results of Comparative Examples 3-4

[0118]

Claims

1. A method for producing white oil for animal vaccines, comprising the following steps: (1) separating a diesel oil feedstock under cutting conditions to obtain a light component and a heavy component; (2) the recombined components enter the adsorption-isomerization reaction unit, contact with the catalyst packed in the adsorption-isomerization reaction unit, and after treatment, a stream A is obtained, which is recycled back to the adsorption-isomerization reaction unit for treatment; the operating conditions of the adsorption reaction in the adsorption-isomerization reaction unit are as follows: temperature is 40-250°C, pressure is 0.01-0.5 MPa, volume space velocity is 0.05-5.0 h -1 -1 -1 ; (3) stopping the heavy component from entering the adsorption-isomerization reaction unit when the refractive index at 20°C of stream A is 0.1% to 5% higher than that of the heavy component; (4) introducing hydrogen into the adsorption-isomerization reaction unit, so that the adsorbate is subjected to isomerization and condensation reduction under the action of a catalyst and hydrogen, and stream B is obtained after treatment; (5) introducing stream B and the light component into a hydrofining reaction unit, so that hydrofining is carried out under the action of hydrogen and a hydrofining catalyst, and gaseous products, light white oil and white oil for animal vaccines are obtained after separation of the reaction effluent; The catalyst comprises an intergrowth molecular sieve of a TON structure molecular sieve and a 5A molecular sieve, an active metal component and an inorganic refractory oxide; and the active metal component is at least one selected from the group consisting of Group VIII noble metals in the Periodic Table.

2. The method for producing white oil for animal vaccines according to claim 1, characterized by: The diesel oil feedstock is at least one selected from the group consisting of hydrocracked diesel oil, hydrotreated diesel oil and hydrorefined diesel oil.

3. The method of producing white oil for animal vaccines according to claim 1, characterized in that: The diesel oil feedstock has a paraffin content of not less than 45 wt%, an aromatic hydrocarbon content of not more than 10 wt%, a condensation point of not more than 5°C, a nitrogen content of not more than 2 ppm and a sulfur content of not more than 10 ppm.

4. The production method of white oil for animal vaccines according to claim 1, characterized in that: The cutting point temperature of the light component and the heavy component in step (1) is 260 to 280°C.

5. The process for producing white oil for animal vaccines according to claim 1, characterized in that: At least one reactor is provided in the adsorption-isomerization reaction unit.

6. The process for producing white oil for animal vaccines according to claim 1, characterized in that: Two reactors are provided in the adsorption-isomerization reaction unit, and the two reactors are connected in parallel and switched to use, so that when the adsorption reaction is completed in one of the reactors and hydrogen is introduced to carry out isomerization and condensation reduction, the heavy component is switched to enter the other reactor to carry out the adsorption reaction.

7. The process for producing white oil for animal vaccines according to claim 1, characterized in that: The operating conditions of the adsorption reaction in the adsorption-isomerization reaction unit in step (2) are as follows: temperature 60-200°C, pressure 0.08-0.1 MPa, volume space velocity 0.1-2.0 h -1 -2.0 h -1 .

8. The process for producing white oil for animal vaccines according to claim 1, characterized in that: In step (3), when the refractive index at 20°C of stream A is 0.5% to 2.5% higher than that of the heavy component, the heavy component is stopped from entering the adsorption-isomerization reaction unit.

9. The process for producing white oil for animal vaccines according to claim 1, characterized in that: The operating conditions of the isomerization and precipitation reaction in the adsorption-isomerization reaction unit in step (4) are as follows: the reaction temperature is 200-420℃, the hydrogen partial pressure is 1.0-20.0 MPa, the volume space velocity is 0.1-10.0 h -1 -1, and the volume ratio of hydrogen to oil is 100:1-1500:

1.

10. The process for producing white oil for animal vaccines according to claim 1, characterized in that: The operating conditions of the isomerization and precipitation reaction in the adsorption-isomerization reaction unit in step (4) are as follows: the reaction temperature is 270-380℃, the hydrogen partial pressure is 3.0-15.0 MPa, the volume space velocity is 0.5-3.0 h -1 -1, and the hydrogen / oil volume ratio is 100:1-400:

1.

11. The process for producing white oil for animal vaccines according to claim 1, characterized in that: The TON structure molecular sieve is intergrown on at least a part of the surface of the 5A molecular sieve at a predetermined surface coverage, and a suitable surface coverage is 0.5% or more and 50% or less.

12. The process for producing white oil for animal vaccines according to claim 1, characterized in that: The TON structure molecular sieve is intergrown on at least a part of the surface of the 5A molecular sieve at a predetermined surface coverage, and a suitable surface coverage is 0.5% or more and 20% or less.

13. The process for producing white oil for animal vaccines according to claim 1, characterized in that: The TON structure molecular sieve is intergrown on at least a part of the surface of the 5A molecular sieve at a predetermined surface coverage, and a suitable surface coverage is 1% or more and 50% or less.

14. The process for producing white oil for animal vaccines according to claim 1, characterized in that: The TON structure molecular sieve is intergrown on at least a part of the surface of the 5A molecular sieve at a predetermined surface coverage, and a suitable surface coverage is 1% or more and 20% or less.

15. The process for producing white oil for animal vaccines as claimed in claim 1, wherein: The specific surface area of the catalyst is 200 m 2 / g to 550 m 2 / g, and the pore volume is 0.25 cm 3 / g to 0.60 cm 3 / g.

16. The process for producing white oil for animal vaccines according to claim 1, characterized in that: The weight ratio of the 5A molecular sieve to the TON structure molecular sieve is 1:80 to 3:

1.

17. The process for producing white oil for animal vaccines according to claim 1, characterized in that: The weight ratio of the 5A molecular sieve to the TON structure molecular sieve is 1:30 to 1:

1.

18. The process for producing white oil for animal vaccines as claimed in claim 1, wherein: The content of the intergrowth molecular sieve is 10 wt% to 90 wt% and the content of the active metal component is 0.05 wt% to 5.0 wt% based on 100 wt% of the total weight of the catalyst.

19. The process for producing white oil for animal vaccines according to claim 1, characterized in that: The content of the embedded molecular sieve is 20wt%-70wt% based on the total weight of the catalyst being 100wt%, and the content of the active metal component is 0.1wt%-1.0wt% based on the metal element.

20. The process for producing white oil for animal vaccines as claimed in claim 1, wherein: The inorganic refractory oxide is selected from one or more of alumina, titania, boria, silica, zirconia and magnesia.

21. The process for producing white oil for animal vaccines according to claim 1, characterized in that: The inorganic refractory oxide is selected from alumina.

22. The process for producing white oil for animal vaccines according to claim 1, characterized in that: The active metal component is selected from at least one of Pt and Pd.

23. The process for producing white oil for animal vaccines as claimed in claim 1, wherein: The active metal component is Pt.

24. The process for producing white oil for animal vaccines as claimed in claim 1, wherein: The TON structure molecular sieve is selected from one or more of ZSM-22, Theta-1, ISI-1, KZ-2 and NU-10.

25. The process for producing white oil for animal vaccines as claimed in claim 1, wherein: The TON structure molecular sieve is selected from ZSM-22.

26. The process for producing white oil for animal vaccines as claimed in claim 1, wherein: The 5A type molecular sieve is selected from 5A molecular sieve.

27. The process for producing white oil for animal vaccines as claimed in claim 1, wherein: The hydrofining operation conditions of the hydrofining reaction unit in step (5) are as follows: reaction temperature 200-350°C, hydrogen partial pressure 1.0-20.0 MPa, volume space velocity 0.1-10.0 h -1 -1, and hydrogen / oil volume ratio 100:1-1500:

1.

28. The process for producing white oil for animal vaccines as claimed in claim 1, wherein: The hydrofining operation conditions of the hydrofining reaction unit in step (5) are as follows: reaction temperature 200-260°C, hydrogen partial pressure 4.5-15.0 MPa, volume space velocity 0.5-1.0 h -1 , hydrogen / oil volume ratio 200:1-800:

1.

29. A production system for realizing the production method of the white oil for animal vaccine according to any one of claims 1-28, comprising: a fractionation unit for receiving a diesel feedstock and separating the diesel feedstock to obtain a light component and a heavy component; an adsorption-isomerization reaction unit for receiving the heavy component from the fractionation unit, the heavy component being subjected to adsorption treatment with a catalyst packed in the adsorption-isomerization reaction unit, a stream A obtained after the treatment being returned to the adsorption-isomerization reaction unit for recycling, when the refractive index at 20℃ of the stream A is 0.1-5% higher than that of the heavy component, the heavy component is stopped from entering the adsorption-isomerization reaction unit, and hydrogen is introduced into the adsorption-isomerization reaction unit, an isomerization and condensation reduction reaction occurring under the action of the catalyst and the hydrogen, a stream B being obtained after the treatment; a hydrofining reaction unit for receiving hydrogen, the stream B from the adsorption-isomerization reaction unit and the light component from the fractionation unit, the hydrofining reaction unit being packed with a hydrofining catalyst, the stream B and the light component being subjected to a hydrofining reaction under the action of the hydrofining catalyst and the hydrogen; a gas-liquid separation zone for receiving a hydrofining reaction effluent from the hydrofining reaction unit, the gas-liquid separation zone separating the hydrofining reaction effluent to obtain a gas phase stream and a liquid phase stream; a fractionation column for receiving the liquid phase stream from the gas-liquid separation zone, the fractionation column separating the liquid phase stream to obtain a light white oil and the white oil for animal vaccine.

30. The production system according to claim 29, characterized in that: The adsorption-isomerization reaction unit is provided with at least one reactor.

31. The production system according to claim 29, characterized in that: The adsorption-isomerization reaction unit is provided with two reactors, and the two reactors are connected in parallel and switched for use.

32. The production system according to claim 29, characterized in that: The hydrofining reaction unit is provided with one or more than one reactor, and the reactor is one or more than one of a fixed bed hydrogenation reactor, a fluidized bed hydrogenation reactor and a slurry bed hydrogenation reactor.

33. The production system according to claim 29, characterized in that: The hydrofining reaction unit is provided with one or more than one reactor, and the reactor is a fixed bed hydrogenation reactor.

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