A method for refining high melting point crude paraffin wax

Abstract

The present invention relates to a method for refining high melting point crude paraffin wax, which adopts a method of adsorption refining and hydrogenation refining in series. The conditions of the adsorption refining are: temperature 50-200°C, volume space velocity 0.1-2.0h ‑1 The conditions of the hydrotreating are: reaction temperature 150-320°C, reaction pressure 2-15MPa, volume space velocity 0.2-2.0h ‑1 , the volume ratio of hydrogen wax is 100-600:1, the adsorbent is formed clay with humic acid added, and the bulk density is 0.5-0.85g / cm 3 . The traditional clay refining device uses powdered clay. After the clay and paraffin or microcrystalline wax are fully stirred and adsorbed in a kettle reactor, they are filtered and separated to remove the waste clay. The equipment used is large, the process is complicated, and the waste clay output is large. The clay adsorption refining process of the present invention uses molded clay, which is continuously adsorbed and refined in a fixed bed reactor. The process is simple and the equipment used is small.

Description

Technical Field

[0001] The invention belongs to the technical field of paraffin refining, and in particular relates to a method for refining high-melting-point crude paraffin. Background Art

[0002] Paraffin wax is widely used in rubber products, tarpaulins, matches and other industrial raw materials. It can also be used as a component and packaging material for food, oral medicines, crayons, candles, carbon paper. Paraffin wax is a petroleum product separated from vacuum distillate or vacuum residue of petroleum. The processing process requires multiple processes such as furfural refining, ketone benzene deoiling and dewaxing. It contains more sulfur and nitrogen compounds, polycyclic aromatic hydrocarbons, colloids, asphaltene and metal impurities. Therefore, the raw wax must be refined to improve its color and light stability and reduce the content of polycyclic aromatic hydrocarbons. Paraffin wax is classified according to melting point. The heavier the distillation range, the higher the melting point, but the impurity content is also higher, and the processing difficulty is also greater.

[0003] The methods currently used for paraffin refining include adsorption refining and hydrogenation refining. Paraffin adsorption refining mainly uses powdered clay kettle reaction intermittent adsorption, which occupies a large area, has a poor operating environment, and causes large paraffin losses. It is currently less used. Paraffin hydrogenation refining mainly removes non-ideal components such as sulfur, nitrogen, and oxygen from paraffin under the action of a hydrogenation refining catalyst under certain temperature, pressure and other process conditions to improve product color, stability, etc. When general paraffin manufacturers process higher melting point paraffin or microcrystalline wax, they generally adopt a production process in which the product is pre-treated with a clay unit and then sent to a hydrogenation unit for deep refining. The process is long and the operating cost is high.

[0004] Chinese patent CN1195830C discloses a paraffin adsorption refining method, which uses hydrogenation refining waste catalyst as adsorbent to purify paraffin. At a refining temperature of 90℃ to 200℃, the wax material is heated for 0.1 to 5.0h. -1 The adsorbent can be regenerated after deactivation. The present invention selects diesel, lubricating oil fractions, and spent catalysts from the hydrorefining of paraffin, which are used for the adsorption refining of paraffin after treatment. The adsorption refining of paraffin can be carried out by a continuous operation method or an intermittent operation method.

[0005] Chinese patent CN1183232C discloses a method for hydrofining petroleum wax, which adopts a fixed bed hydrofining method with a single reactor and dual catalyst beds, including a method of refining petroleum wax by using two catalyst graded loading methods, Mo-Ni catalyst and W-Ni catalyst. The operating conditions for hydrofining of paraffin wax are as follows: the hydrogen partial pressure of the first bed is 4-10MPa, the reaction temperature is 270-330℃, and the hydrogen-wax volume ratio is 100-1000; the hydrogen partial pressure of the second bed is 4-10MPa, the reaction temperature is 230-270℃; the total volume space velocity of the two beds is 0.5-3.0h-1 .

[0006] Chinese patent CN 1064701C discloses a composite adsorbent formed by mixing catalytic cracking waste catalyst and activated clay for the refining of paraffin. The process is intermittent operation and the composite adsorbent cannot be regenerated.

[0007] Chinese patent CN1038144C uses adsorption to purify rice bran wax and its natural wax. The selected adsorbents are composite adsorbents such as Al2O3, silica, polyamide, and methacrylate resin. The particle size is 100-200 mesh, the refined wax yield is 74%-91%, and the product is white or light yellow. Saturated hydrocarbons (such as petroleum ether) are used as solvents, and the solution is prepared with wax for refining, and the adsorption column is washed with the solvent. The product is obtained by distillation, the solvent is recovered, and the adsorbent can be recycled after regeneration. This method uses solvent as a diluent, so the separation of solvent increases energy consumption.

[0008] Chinese patent CN 1062585C discloses a method for producing lubricating oil base oil and food paraffin wax, wherein the cracked tail oil is dewaxed and deoiled by solvent to separate the paraffin component and oil in the raw material, and then the bleaching clay is used to obtain qualified lubricating oil base oil and food paraffin wax products. The refining temperature in the bleaching clay refining process is 100-130°C, the preferred refining temperature is 105-115°C, the amount of bleaching clay is 1-5wt% of the raw material amount, the more suitable addition amount is 2wt%, the refining time is 20-50 minutes, and the more suitable refining time is 30 minutes.

[0009] Chinese patent CN 103865580A discloses a method for preparing food-grade microcrystalline wax, comprising mixing a heavy lubricating oil component at 480°C to 750°C with a ketone-benzene dewaxing solvent, cooling the mixture to below -15°C, filtering to obtain a dewaxing filtrate and deoiled wax, mixing the obtained deoiled wax with kaolin, wherein the mixing mass of the kaolin is 2% to 5%, the mixing temperature is 110°C to 130°C, stirring for 10 to 30 minutes, filtering to remove the kaolin, and obtaining a food-grade microcrystalline wax product.

[0010] Chinese patent CN105985806B discloses a method for improving the smell and appearance of paraffin wax. The deoiled wax after the solvent is recovered by the solvent dewaxing device is contacted with kaolin, and the mixture is separated to obtain kaolin refined wax. Kaolin refining refers to adding kaolin to the deoiled wax, and after mixing, the kaolin is porous, has a large specific surface area, and is easy to adsorb polar substances to absorb a small amount of aromatic hydrocarbons, colloids, solvents and mechanical impurities in the deoiled wax, and the mixture is separated to obtain kaolin refined wax to improve the color, light stability and smell of paraffin wax. The kaolin refining temperature is 110℃~170℃, and more preferably 120℃~160℃; the amount of kaolin used is 0.2%~8% of the mass fraction of the deoiled wax, and more preferably 0.5%~7%.

[0011] Chinese patent CN113322099A discloses a method for producing microcrystalline wax with a high drop melting point, wherein light deasphalted oil is first subjected to furfural refining and ketone-benzene dewaxing and deoiling treatment to obtain crude microcrystalline wax, and then the crude microcrystalline wax is refined by a combined process of bleaching clay adsorption and hydrogenation, and finally the high drop melting point microcrystalline wax is obtained after separation, stripping and drying. The amount of bleaching clay added is 3-5wt% of the crude microcrystalline wax, and more preferably 3-4wt% of the crude microcrystalline wax. Summary of the invention

[0012] Based on the above, the object of the present invention is to provide a method for refining high melting point crude paraffin wax, which has the advantages of simple process and less equipment used.

[0013] To this end, the present invention provides a method for refining high melting point crude paraffin, which adopts a method of adsorption refining and hydrogenation refining in series, wherein the conditions of the adsorption refining are: temperature 50-200°C, volume space velocity 0.1-2.0h -1 The conditions of the hydrotreating are: reaction temperature 150-320°C, reaction pressure 2-15MPa, volume space velocity 0.2-2.0h -1 , the volume ratio of hydrogen wax is 100-600:1, the adsorbent is formed clay with humic acid added, and the bulk density is 0.5-0.85g / cm 3 .

[0014] Specifically, the product after white clay adsorption refining is mixed with circulating hydrogen and enters into the hydrogenation refining reactor through a heating furnace.

[0015] Specifically, the conventional clay refining device uses powdered clay, and the clay and paraffin or microcrystalline wax are fully stirred and adsorbed in a kettle reactor, and then filtered and separated to remove the waste clay. The equipment used is large, the process is complicated, and the waste clay output is large. The clay adsorption refining process of the present invention uses formed clay, and continuously adsorbs and purifies in a fixed bed reactor, which has a simple process and uses less equipment.

[0016] In the method for refining high melting point crude paraffin wax of the present invention, it is preferred that the adsorption refining adopts two or two groups of fixed bed reactors, and the fixed bed reactors are connected in parallel or switched. The deactivated adsorption refining agent is centrally processed.

[0017] The method for refining high melting point crude paraffin described in the present invention, wherein preferably, the hydrogenation refining catalyst adopts a W-Ni system paraffin hydrogenation refining catalyst, and further preferably, the W-Ni system paraffin hydrogenation refining catalyst has a bulk density of 0.5-1.0 g / ml, a NiO content of 1.5-4.5wt%, a WO3 content of 20-40wt%, and an Al2O3 content of 55-75wt%.

[0018] The method for refining high melting point crude paraffin wax of the present invention is preferably that the conditions for the hydrogenation refining are: reaction temperature 280-310°C, reaction pressure 5-8MPa, volume space velocity 0.3-0.6h -1 , hydrogen wax volume ratio 100~400:1.

[0019] In the method for refining high melting point crude paraffin wax of the present invention, it is preferred that the hydrofining adopts two or two groups of reactors, and the reactors are connected in parallel or switched. The deactivated hydrofining catalyst is centrally treated.

[0020] The method for refining high melting point crude paraffin wax of the present invention is preferably such that the method for preparing the adsorption refining agent used in the adsorption refining comprises the following steps:

[0021] (1) Mixing powdered activated clay, a binder, humic acid, and sesbania powder uniformly;

[0022] (2) dissolving nitric acid in deionized water to prepare a nitric acid solution, adding the nitric acid solution to the mixture obtained in step (1), kneading evenly, and extruding to form;

[0023] (3) Drying and roasting the shaped mixture obtained in step (2) to obtain an adsorption refining agent with a bulk density of 0.5 to 0.85 g / cm 3 .

[0024] In the method for refining high melting point crude paraffin wax of the present invention, it is preferred that the binder is alumina or silica sol.

[0025] The method for refining high melting point crude paraffin wax of the present invention is preferably such that in step (1), the mass ratio of powdered activated clay, binder, humic acid and sesbania powder is 30-95:1-30:10-50:1-10.

[0026] The method for refining high melting point crude paraffin wax of the present invention is preferably characterized in that the drying conditions are: temperature 120-130° C., time 4-5 hours.

[0027] The method for refining high melting point crude paraffin wax of the present invention is preferably characterized in that the calcination conditions are: temperature 500-550° C., time 4-5 hours.

[0028] The beneficial effects of the present invention are as follows:

[0029] Compared with the traditional process, the production process of the present invention has fewer equipment, a small footprint for the adsorption refining reactor, flexible operation for replacing the adsorbent, low clay usage, and low paraffin loss. In addition, the adsorption refining and hydrogenation refining are operated continuously, and the production efficiency is high. DETAILED DESCRIPTION

[0030] The following is a detailed description of the embodiments of the present invention: This embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation method and process are given, but the protection scope of the present invention is not limited to the following embodiments. The experimental methods in the following embodiments without specifying specific conditions are usually carried out under conventional conditions, and the unspecified % is weight %.

[0031] The refining method of high melting point crude paraffin provided by the present invention adopts a method of adsorption refining and hydrogenation refining in series, and the conditions of the adsorption refining are: temperature 50-200°C, volume space velocity 0.1-2.0h -1 The conditions of the hydrotreating are: reaction temperature 150-320°C, reaction pressure 2-15MPa, volume space velocity 0.2-2.0h -1 , the volume ratio of hydrogen wax is 100-600:1, the adsorbent is formed clay with humic acid added, and the bulk density is 0.5-0.85g / cm 3 .

[0032] Specifically, the product after white clay adsorption refining is mixed with circulating hydrogen and enters into the hydrogenation refining reactor through a heating furnace.

[0033] Specifically, the conventional clay refining device uses powdered clay, and the clay and paraffin or microcrystalline wax are fully stirred and adsorbed in a kettle reactor, and then filtered and separated to remove the waste clay. The equipment used is large, the process is complicated, and the waste clay output is large. The clay adsorption refining process of the present invention uses formed clay, and continuously adsorbs and purifies in a fixed bed reactor, which has a simple process and uses less equipment.

[0034] In some embodiments, preferably, the adsorption refining uses two or two groups of fixed bed reactors, and the fixed bed reactors are connected in parallel or switched. The deactivated adsorption refining agent is centrally processed.

[0035] In some embodiments, it is preferred that the hydrotreating catalyst adopts a W-Ni system paraffin hydrotreating catalyst. Further preferably, the W-Ni system paraffin hydrotreating catalyst has a bulk density of 0.5-1.0 g / ml, a NiO content of 1.5-4.5 wt%, a WO3 content of 20-40 wt%, and an Al2O3 content of 55-75 wt%.

[0036] In some embodiments, preferably, the conditions of the hydrofining are: reaction temperature 280-310°C, reaction pressure 5-8MPa, volume space velocity 0.3-0.6h -1 , hydrogen wax volume ratio 100~400:1.

[0037] In some embodiments, it is preferred that the hydrofining process uses two or two groups of reactors, which are connected in parallel or switched. The deactivated hydrofining catalyst is centrally treated.

[0038] In some embodiments, preferably, the method for preparing the adsorption refining agent used in the adsorption refining comprises the following steps:

[0039] (1) Mixing powdered activated clay, a binder, humic acid, and sesbania powder uniformly;

[0040] (2) dissolving nitric acid in deionized water to prepare a nitric acid solution, adding the nitric acid solution to the mixture obtained in step (1), kneading evenly, and extruding to form;

[0041] (3) Drying and roasting the shaped mixture obtained in step (2) to obtain an adsorption refining agent with a bulk density of 0.5 to 0.85 g / cm 3 .

[0042] In some embodiments, preferably, the binder is alumina or silica sol.

[0043] In some embodiments, preferably, in step (1), the mass ratio of powdered activated clay, binder, humic acid and sesbania powder is 30-95: 1-30: 10-50: 1-10.

[0044] In some embodiments, preferably, the drying conditions are: temperature 120-130° C., time 4-5 hours.

[0045] In some embodiments, preferably, the calcination conditions are: temperature 500-550° C., time 4-5 hours.

[0046] The raw material used in the following examples and comparative examples is No. 68 crude paraffin, which has an oil content of 2.05 wt%, a melting point of 69° C., a color (Sai) of -17, and a light stability of >9.

[0047] Example 1

[0048] (1) Preparation of adsorption refining agent JZ-1

[0049] (a) 100 g of powdered activated clay, 5 g of a binder, 20 g of humic acid, and 5 g of sesbania powder were mixed uniformly;

[0050] (b) dissolving 5 g of nitric acid in 45 g of deionized water to prepare a nitric acid solution, adding the nitric acid solution to the mixture obtained in step (a), kneading the mixture evenly, and extruding the mixture;

[0051] (c) The shaped mixture obtained in step (b) was dried at 120° C. for 4 hours, and then calcined at 500° C. for 4 hours to obtain an adsorption refining agent, which was designated as JZ-1.

[0052] (2) Paraffin wax refining process

[0053] Take 80ml of adsorption refining agent and put it into a 200ml reactor. The adsorption refining temperature is 120-130℃, and the 68# crude paraffin is heated for 0.4h. -1 The adsorption product is mixed with hydrogen and enters the hydrogenation reactor equipped with W-Ni system paraffin hydrogenation catalyst (bulk density 0.75g / ml, NiO content 3.1wt%, WO3 content 28.5wt%, Al2O3 content 66.5wt%). The reaction temperature is 290℃, the reaction pressure is 7MPa, and the volume space velocity is 0.3h -1 , under the process conditions of a hydrogen-wax volume ratio of 300:1, a hydrogenation refining reaction was carried out, and the product wax contained 1.96wt% oil, a melting point of 69°C, a color (Sampo) of 26, and a light stability of 5.

[0054] Example 2

[0055] (1) Preparation of adsorption refining agent JZ-2

[0056] (a) 110 g of powdered activated clay, 8 g of a binder, 25 g of humic acid, and 5 g of sesbania powder were mixed uniformly;

[0057] (b) dissolving 5 g of nitric acid in 45 g of deionized water to prepare a nitric acid solution, adding the nitric acid solution to the mixture obtained in step (a), kneading the mixture evenly, and extruding the mixture;

[0058] (c) The shaped mixture obtained in step (b) was dried at 120° C. for 4 hours, and then calcined at 500° C. for 4 hours to obtain an adsorption refining agent, which was designated as JZ-2.

[0059] (2) Paraffin wax refining process

[0060] Take 80ml of adsorption refining agent and put it into a 200ml reactor. The adsorption refining temperature is 120-130℃, and the 68# crude paraffin is heated for 0.4h. -1 The adsorption product is mixed with hydrogen and enters the hydrogenation reactor equipped with W-Ni system paraffin hydrogenation catalyst (bulk density 0.75g / ml, NiO content 3.1wt%, WO3 content 28.5wt%, Al2O3 content 66.5wt%). The reaction temperature is 290℃, the reaction pressure is 7MPa, and the volume space velocity is 0.3h -1, under the process conditions of a hydrogen-wax volume ratio of 300:1, a hydrogenation refining reaction was carried out, and the product wax contained 1.98wt% oil, a melting point of 69°C, a color (Sampo) of 27, and a light stability of 5.

[0061] Example 3

[0062] (1) Preparation of adsorption refining agent JZ-3

[0063] (a) 100 g of powdered activated clay, 5 g of a binder, 20 g of humic acid, and 5 g of sesbania powder were mixed uniformly;

[0064] (b) dissolving 5 g of nitric acid in 45 g of deionized water to prepare a nitric acid solution, adding the nitric acid solution to the mixture obtained in step (a), kneading the mixture evenly, and extruding the mixture;

[0065] (c) The shaped mixture obtained in step (b) was dried at 120° C. for 4 hours, and then calcined at 500° C. for 4 hours to obtain an adsorption refining agent, which was designated as JZ-3.

[0066] (2) Paraffin wax refining process

[0067] Take 80ml of adsorption refining agent and put it into a 200ml reactor. The adsorption refining temperature is 120-130℃, and the 68# crude paraffin is heated for 1.0h. -1 The adsorption product is mixed with hydrogen and enters the hydrogenation reactor equipped with W-Ni system paraffin hydrogenation catalyst (bulk density 0.75g / ml, NiO content 3.1wt%, WO3 content 28.5wt%, Al2O3 content 66.5wt%). The reaction temperature is 290℃, the reaction pressure is 7MPa, and the volume space velocity is 0.3h -1 , under the process conditions of a hydrogen-wax volume ratio of 300:1, a hydrogenation refining reaction was carried out, and the product wax contained 1.99wt% oil, a melting point of 69°C, a color (Sampo) of 22, and a light stability of 6.

[0068] Example 4

[0069] 80 ml of the adsorption refining agent prepared in Example 1 was placed in a 200 ml reactor, the adsorption refining temperature was 120-130°C, and the 68# crude paraffin was heated for 0.4 h. -1 The volume space velocity passed through the adsorption reactor, and the product wax contained 2.02wt% oil, had a melting point of 69°C, a color (Sai) of No. 4, and a light stability of > No. 9.

[0070] Comparative Example 1

[0071] Take 80ml of clay powder and put it into a 200ml reactor. The adsorption refining temperature is 120-130℃, and the 68# crude paraffin is heated for 0.4h. -1The adsorption product is mixed with hydrogen and enters the hydrogenation reactor equipped with W-Ni system paraffin hydrogenation catalyst (bulk density 0.75g / ml, NiO content 3.1wt%, WO3 content 28.5wt%, Al2O3 content 66.5wt%). The reaction temperature is 290℃, the reaction pressure is 7MPa, and the volume space velocity is 0.3h -1 , under the process conditions of a hydrogen-wax volume ratio of 300:1, a hydrogenation refining reaction was carried out, and the product wax contained 1.99wt% oil, a melting point of 69°C, a color (Sampo) of No. 19, and a light stability of No. 7.

[0072] Comparative Example 2

[0073] The crude paraffin No. 68 was directly fed into a hydrogenation reactor equipped with a W-Ni system paraffin hydrogenation catalyst (bulk density 0.75 g / ml, NiO content 3.1 wt%, WO3 content 28.5 wt%, Al2O3 content 66.5 wt%) without adsorption refining. The reaction temperature was 290 ° C, the reaction pressure was 7 MPa, and the volume space velocity was 0.3 h -1 , hydrogen wax volume ratio of 300:1 process conditions, hydrogenation refining reaction was carried out, the product wax oil content 1.99wt%, melting point 69 ° C, color (Sampo) 17, light stability 8.

[0074] Comparative Example 3

[0075] Take 80ml of white clay powder and put it into a 200ml reactor. The adsorption refining temperature is 120-130℃. No. 68 crude paraffin passes through the adsorption reactor at a volume space velocity of 0.4h-1. The product wax contains 2.01wt% oil, has a melting point of 69℃, a color (Sai) of No. 0, and light stability > No. 9.

[0076] Comparative Example 4

[0077] (1) Preparation of adsorption refining agent JZ-4

[0078] The preparation of the adsorption refining agent is the same as that of JZ-1 in Example 1, except that humic acid is not added during the preparation of the adsorption refining agent.

[0079] (2) Paraffin wax refining process

[0080] Take 80ml of adsorption refining agent and put it into a 200ml reactor. The adsorption refining temperature is 120-130℃, and the 68# crude paraffin is heated for 0.4h. -1 The adsorption product is mixed with hydrogen and enters the hydrogenation reactor equipped with W-Ni system paraffin hydrogenation catalyst (bulk density 0.75g / ml, NiO content 3.1wt%, WO3 content 28.5wt%, Al2O3 content 66.5wt%). The reaction temperature is 290℃, the reaction pressure is 7MPa, and the volume space velocity is 0.3h-1 , hydrogenation refining reaction was carried out under the process conditions of a hydrogen-wax volume ratio of 300:1, and the product wax contained 2.02wt% oil, a melting point of 69°C, a color (Sampo) of 24, and a light stability of 6.

[0081] Comparative Example 5

[0082] The No. 68 crude paraffin was dissolved and added into a 120°C reactor, stirred, and 2% of the mass of the paraffin was added with clay, stirred for 1 hour, and then filtered. The resulting paraffin entered a hydrogenation reactor equipped with a W-Ni system paraffin hydrogenation catalyst (bulk density 0.75g / ml, NiO content 3.1wt%, WO3 content 28.5wt%, Al2O3 content 66.5wt%), and the reaction temperature was 290°C, the reaction pressure was 7MPa, and the volume space velocity was 0.3h -1 , under the process conditions of a hydrogen-wax volume ratio of 300:1, a hydrogenation refining reaction was carried out, and the product wax contained 2.02wt% oil, a melting point of 69°C, a color (Sampo) of 22, and a light stability of 7.

[0083] Comparative Example 6

[0084] The No. 68 crude paraffin was dissolved and added into a 120°C reactor, stirred, and 6% of the paraffin mass of white clay was added, stirred for 1 hour, and then filtered. The resulting paraffin entered a hydrogenation reactor equipped with a W-Ni system paraffin hydrogenation catalyst (bulk density 0.75g / ml, NiO content 3.1wt%, WO3 content 28.5wt%, Al2O3 content 66.5wt%), and the reaction temperature was 290°C, the reaction pressure was 7MPa, and the volume space velocity was 0.3h -1 , under the process conditions of a hydrogen-wax volume ratio of 300:1, a hydrogenation refining reaction was carried out, and the product wax contained 1.99wt% oil, a melting point of 69°C, a color (Sampo) of 26, and a light stability of 5.

[0085] Comparative Example 7

[0086] The No. 68 crude paraffin was dissolved and added into a 120°C reactor, stirred, and 10% of the paraffin mass of white clay was added, stirred for 1 hour, and then filtered. The resulting paraffin entered a hydrogenation reactor equipped with a W-Ni system paraffin hydrogenation catalyst (bulk density 0.75g / ml, NiO content 3.1wt%, WO3 content 28.5wt%, Al2O3 content 66.5wt%), and the reaction temperature was 290°C, the reaction pressure was 7MPa, and the volume space velocity was 0.3h -1 , under the process conditions of a hydrogen-wax volume ratio of 300:1, a hydrogenation refining reaction was carried out, and the product wax contained 1.98wt% oil, a melting point of 69°C, a color (Sampo) of 26, and a light stability of 5.

[0087] Table 1 Physicochemical properties of adsorption refining agents in various examples

[0088]

[0089] Table 2 Processing technology and product properties of each embodiment

[0090]

[0091]

[0092] Table 1 shows the physicochemical properties of the adsorption refiner in each example. It can be seen that the properties of the powdered clay and the adsorption refiner are similar, except that the pore size of the adsorption refiner is larger. A large pore size is conducive to the adsorption of colloid in the raw material.

[0093] Table 2 shows the processing technology and product properties of each embodiment. It can be seen from the comparison between Example 1 and Comparative Example 1 that the improvement of paraffin color by adsorption refining agent is significantly better than that of clay powder. It can be seen from the comparison between each embodiment and Comparative Example 2 that the color of paraffin can be improved to a certain extent only by hydrogenation refining, but the degree is limited. The reason may be that the condensation molecules and colloids in paraffin cannot be removed by hydrogenation. Adsorption refining is an important means to improve paraffin products. It can be seen from the comparison between Example 4 and Comparative Example 3 that under the condition of no hydrogenation refining process, the effect of adsorption refining agent is better than that of powdered clay, indicating that the adsorption refining agent is improved after molding modification. The comparison between Example 1 and Comparative Example 4 shows that the addition of humic acid during the preparation of the adsorption refining agent can improve the color of paraffin, which is related to the strong adsorption capacity of humic acid. It can be seen from the comparison between Examples 1 and 2 and Comparative Examples 6 and 7 that the effect achieved by adsorption refining and intermittent operation of clay is basically the same, but the intermittent operation of clay has a long reaction time and low efficiency.

[0094] In order to further investigate the refining effect, a light test was conducted on the above products. The above samples were exposed to sunlight for 30 days. Table 3 shows the properties of each product after 30 days of exposure.

[0095] Table 3 Properties of the products of each embodiment and comparative example after 30 days of illumination

[0096]

[0097] From the comparison between Example 1 and Comparative Example 1 in Table 3, it can be seen that after 30 days of light exposure, the color and stability of the paraffin wax treated with the adsorption refiner are significantly better than those treated with white clay, indicating that the adsorption refiner can improve the light resistance of the paraffin wax, which is beneficial to the long-term preservation of the product.

[0098] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the present invention.

Claims

1. A method for refining high melting point crude paraffin wax, characterized in that: Adsorption refining and hydrorefining are connected in series. The adsorption refining conditions are: temperature 50-200°C, volume space velocity 0.1-2.0h -1 The conditions of the hydrotreating are: reaction temperature 150-320°C, reaction pressure 2-15MPa, volume space velocity 0.2-2.0h -1 , the volume ratio of hydrogen wax is 100-600:1, the adsorption refining adopts an adsorption refining agent, the adsorption refining agent is a molded white clay added with humic acid, and the bulk density is 0.5-0.85g / cm 3 ; The preparation method of the adsorption fine preparation comprises the following steps: (1) Mixing powdered activated clay, a binder, humic acid, and sesbania powder uniformly; (2) dissolving nitric acid in deionized water to prepare a nitric acid solution, adding the nitric acid solution to the mixture obtained in step (1), kneading the mixture evenly, and then extruding it into a shape; (3) drying and calcining the shaped mixture obtained in step (2) to obtain an adsorption refining agent; The hydrotreating process uses a W-Ni system paraffin hydrotreating catalyst.

2. The method for refining high melting point crude paraffin according to claim 1, characterized in that: The adsorption refining adopts two or two groups of fixed bed reactors, and the fixed bed reactors are connected in parallel or switched for use.

3. The method for refining high melting point crude paraffin according to claim 1, characterized in that, The W-Ni system paraffin hydrorefining catalyst has a bulk density of 0.5-1.0 g / ml, a NiO content of 1.5-4.5 wt %, a WO 3 content of 20-40 wt %, and an Al 2 O 3 content of 55-75 wt %.

4. The method for refining high melting point crude paraffin according to claim 1, characterized in that: The conditions of the hydrofining are: reaction temperature 280-310°C, reaction pressure 5-8MPa, volume space velocity 0.3-0.6h -1 , hydrogen wax volume ratio 100~400:

1.

5. The method for refining high melting point crude paraffin according to claim 1, characterized in that: The hydrotreating process uses two or two groups of reactors, which are connected in parallel or switched for use.

6. The method for refining high melting point crude paraffin according to claim 1, characterized in that: The binder is alumina or silica sol.

7. The method for refining high melting point crude paraffin according to claim 1, characterized in that: In step (1), the mass ratio of powdered activated clay, binder, humic acid and sesbania powder is 30-95:1-30:10-50:1-10.

8. The method for refining high melting point crude paraffin according to claim 1, characterized in that: The drying conditions are: temperature 120-130° C., time 4-5 hours.

9. The method for refining high melting point crude paraffin according to claim 1, characterized in that: The calcination conditions are: temperature 500-550° C., time 4-5 hours.

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