CN112852481A - Fischer-Tropsch wax decoloring method - Google Patents
Fischer-Tropsch wax decoloring method Download PDFInfo
- Publication number
- CN112852481A CN112852481A CN202011604777.0A CN202011604777A CN112852481A CN 112852481 A CN112852481 A CN 112852481A CN 202011604777 A CN202011604777 A CN 202011604777A CN 112852481 A CN112852481 A CN 112852481A
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- fischer
- tropsch wax
- catalyst
- spent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a process for the decolorization of fischer-tropsch wax, comprising: (1) adding an adsorbent A into the molten Fischer-Tropsch wax crude product for first adsorption; adding an adsorbent B for second adsorption to obtain a mixed system; (2) under the condition of keeping the Fischer-Tropsch wax crude product in a molten state, adding a separation liquid I into the mixed system, and then aging and filtering to obtain refined Fischer-Tropsch wax, a separation liquid II and an adsorbent; wherein the adsorbent A comprises clay; the adsorbent B comprises a spent MTP catalyst. The method provided by the invention can improve the chroma of the treated Fischer-Tropsch wax and the yield of the refined Fischer-Tropsch wax, and is simple and has high economic benefit.
Description
Technical Field
The invention relates to Fischer-Tropsch wax decoloration, in particular to a Fischer-Tropsch wax decoloration method.
Background
The Fischer-Tropsch wax is a hydrocarbon product which is synthesized by using synthesis gas under the action of a catalyst, has the molecular weight of 200-2000 and is mainly composed of normal hydrocarbon, and has the characteristics of low sulfur, low nitrogen, low aromatic hydrocarbon content and the like. The Fischer-Tropsch wax can be divided into high melting point, medium melting point and low melting point according to the drop melting point. The quality of the medium-low melting point Fischer-Tropsch wax (the drop melting point is less than 80 ℃) can reach the quality of refined paraffin wax after deoiling treatment, and the medium-low melting point Fischer-Tropsch wax can replace the paraffin wax in the fields of candles, emulsified wax, packaging wax, rubber protective wax and the like. The high melting point Fischer-Tropsch wax (the drop melting point is more than or equal to 80 ℃) is mainly used in the fields of PVC processing, ink coating and rubber protection and can replace imported Fischer-Tropsch wax and polyethylene wax.
In the synthesis or processing process of the Fischer-Tropsch wax, iron and cobalt are mainly used as main catalysts, and impurities such as catalysts, catalyst carriers and the like are easily left in a Fischer-Tropsch wax sample, so that the color number of the Fischer-Tropsch wax is increased (the color is darkened), and the appearance and the product quality of the Fischer-Tropsch wax product are influenced. It is therefore necessary to remove the catalyst, catalyst support, colour species and impurities from the fischer-tropsch wax.
CN105482849A discloses a method for improving the chromaticity of Fischer-Tropsch wax, which comprises the steps of firstly carrying out continuous high vacuum distillation on the Fischer-Tropsch wax, and then adopting an adsorbent to adsorb the Fischer-Tropsch wax, wherein the method has complicated steps and high requirements on operating conditions.
CN109486529A discloses a liquid black wax filtering process and a filtering system, the process comprises the steps of mixing black wax and white clay in proportion, carrying out initial sedimentation, sending into a first reaction kettle, adding a decolorizing agent and white clay, fully stirring, carrying out first-stage filtration, putting the material subjected to first-stage filtration into a second reaction kettle, adding the decolorizing agent, fully stirring and filtering to obtain the decolorizing Fischer-Tropsch wax. The technology needs long standing time, low production efficiency, needs multistage adsorption and has complex filtering process.
CN1161367A discloses a method for refining paraffin by using a composite adsorbent, which mainly adopts activated clay and FCC spent catalyst as the composite adsorbent to refine paraffin, and adopts the composite adsorbent to adsorb pigment in the paraffin to prepare refined paraffin.
In summary, when the fischer-tropsch wax is decolorized with the clay, the fischer-tropsch wax is first subjected to pretreatment (such as sedimentation and distillation), and then the fischer-tropsch wax is adsorbed by the clay adsorbent, and the decolorization effect needs to be improved.
Disclosure of Invention
The invention aims to solve the problems of complex Fischer-Tropsch wax decoloring process and poor decoloring effect in the prior art, and provides a Fischer-Tropsch wax decoloring method.
The inventor of the invention finds that the adoption of the argil as the adsorbent has the following defects in the process of researching the Fischer-Tropsch wax: (1) the particle size of the argil is small, the supporting effect is poor, when the Fischer-Tropsch wax is adsorbed, impurities in the Fischer-Tropsch wax can be adsorbed, and the Fischer-Tropsch wax can be adsorbed into gaps of the argil, so that the gaps of the argil are blocked, the adsorption effect of the impurities in the Fischer-Tropsch wax can be influenced, the loss of the Fischer-Tropsch wax is caused, and the service life of the argil is shortened; (2) because the gaps of the argil are blocked, the pressure difference of the filter is large during filtering, so that the production energy consumption and the production cost are increased; (3) because the filtering effect is poor, multi-stage adsorption and filtering are required, and the treatment period is long; (4) the clay has small particle size, is easy to scatter in the using process and causes pollution to the environment. The waste MTP catalyst and the carclazyte and other adsorbents are combined according to a specific proportion, the waste MTP catalyst can provide a framework for the carclazyte and other adsorbents to adhere, disperse and support, the porosity of a filter cake during filtration is increased, and the carclazyte and other adsorbents are kept in a loose porous state, so that the flow resistance is reduced, and the filtration efficiency is improved.
In order to achieve the above object, the present invention provides a method for decolorizing fischer-tropsch wax, comprising:
(1) adding an adsorbent A into the molten Fischer-Tropsch wax crude product for first adsorption; adding an adsorbent B for second adsorption to obtain a mixed system; or
Adding an adsorbent B into the molten Fischer-Tropsch wax crude product to directly perform second adsorption to obtain a mixed system;
(2) under the condition of keeping the Fischer-Tropsch wax crude product in a molten state, adding a separation liquid I into the mixed system, and then aging and filtering to obtain refined Fischer-Tropsch wax, a separation liquid II and an adsorbent;
wherein the adsorbent A comprises clay;
the adsorbent B comprises a spent MTP catalyst.
Through the technical scheme, the waste MTP catalyst can provide a framework for the attachment, dispersion and support of the adsorbents such as the argil and the like, so that the adsorbents such as the argil and the like are kept in a loose and porous state, the porosity of a filter cake during filtration can be increased, and the flow resistance is reduced; the method of the invention can not only improve the filtering effect and remove the colored substances in the Fischer-Tropsch wax, but also improve the filtering capacity and reduce the filtering cost; the carrying amount of the Fischer-Tropsch wax in the clay can be reduced, and the loss of the Fischer-Tropsch wax is reduced; the method of aging firstly and then filtering is adopted, so that the treatment capacity of the filter can be reduced, and the production capacity of the filter is improved.
The method of the invention can improve the chroma of the treated Fischer-Tropsch wax and the yield of the refined Fischer-Tropsch wax, and has the advantages of simple method and higher economic benefit.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously mentioned, the present invention provides a process for the decolorization of fischer-tropsch wax, the process comprising:
(1) adding an adsorbent A into the molten Fischer-Tropsch wax crude product for first adsorption; adding an adsorbent B for second adsorption to obtain a mixed system; or
Adding an adsorbent B into the molten Fischer-Tropsch wax crude product to directly perform second adsorption to obtain a mixed system;
(2) under the condition of keeping the Fischer-Tropsch wax crude product in a molten state, adding a separation liquid I into the mixed system, and then aging and filtering to obtain refined Fischer-Tropsch wax, a separation liquid II and an adsorbent;
wherein the adsorbent A comprises clay; the adsorbent B comprises a spent MTP catalyst.
According to the invention, firstly, the Fischer-Tropsch wax crude product is subjected to first adsorption through the adsorbent A, and then the adsorbent B containing the waste MTP catalyst is used for second adsorption, so that the decolorization efficiency of the Fischer-Tropsch wax can be obviously improved, and then the reaction liquid is added for sedimentation, so that the Fischer-Tropsch wax in the pores of the adsorbent can be replaced, and the adsorbent and the Fischer-Tropsch wax crude product are separated, thereby improving the subsequent filtration efficiency and the yield of refined Fischer-Tropsch wax; wherein, the first adsorption and the second adsorption are required to be carried out under the condition of keeping the Fischer-Tropsch wax crude product in a molten state, and the adsorption time depends on the content of impurities in the Fischer-Tropsch wax, and the inventor finds that when the first adsorption condition is satisfied: the temperature is 40-200 ℃, the time is 0-3h, and the second adsorption condition meets: the Fischer-Tropsch wax has better decolorizing effect when the temperature is 40-200 ℃ and the time is 0.2-2 h.
The waste MTP catalyst is compounded with other adsorbents to adsorb the Fischer-Tropsch wax crude product, so that the impurities of aliphatic hydrocarbon and alicyclic hydrocarbon in the Fischer-Tropsch wax can be removed, and the impurities of the catalyst, a catalyst carrier and the like in the Fischer-Tropsch wax can be effectively removed, so that the decoloring efficiency of the Fischer-Tropsch wax and the quality of refined Fischer-Tropsch wax are effectively improved.
In the invention, the waste MTP catalyst is ZSM-5 catalyst particles eliminated in the production of propylene from methanol, and the aperture of the ZSM-5 catalyst is
The specific surface area is 300-500m2/g；
Preferably, the spent ZSM-5 catalyst includes 75 to 90 wt% SiO based on the total amount of the spent ZSM-5 catalyst210-25% by weight of Al2O30-1% by weight of Na2O; more preferably, the carbon content of the spent ZSM-5 catalyst is in the range of 0 to 10 wt%, more preferably 0 to 5 w%.
According to the invention, under preferred conditions, the adsorbent B comprises a spent MTP catalyst, optionally clay, optionally activated carbon and optionally diatomaceous earth; further preferably, the adsorbent B comprises, based on the total amount of the adsorbent B: 10-50 wt% of waste MTP catalyst, 0-80 wt% of clay, 0-90 wt% of active carbon and 0-50 wt% of diatomite. Particularly preferably, the adsorbent B comprises, based on the total amount of the adsorbent B: 20-30 wt% of waste MTP catalyst, 10-20 wt% of clay, 20-40 wt% of activated carbon and 20-40 wt% of diatomite.
In a preferred embodiment of the present invention, the adsorbent B comprises, based on the total amount of the adsorbent B: 20-50 wt% of waste MTP catalyst, 20-50 wt% of activated carbon and 20-30 wt% of diatomite.
In a preferred embodiment of the present invention, the adsorbent B comprises, based on the total amount of the adsorbent B: 10-50 wt% of waste MTP catalyst, 30-80 wt% of clay and 0-20 wt% of active carbon.
In a preferred embodiment of the present invention, the adsorbent B comprises, based on the total amount of the adsorbent B: 10-20 wt% of waste MTP catalyst and 80-90 wt% of clay.
According to the invention, in order to improve the decolorization effect of the Fischer-Tropsch wax crude product, under the preferable conditions, the content of the adsorbent A is 0-40 wt% and the content of the adsorbent B is 60-100 wt% based on the total amount of the adsorbent A and the adsorbent B; further preferably, the total amount of adsorbent a and adsorbent B used is 0.5-10 wt% of the crude fischer-tropsch wax.
According to the invention, the adsorbent and the Fischer-Tropsch wax crude product can be separated by adding the separation liquid, so that the subsequent filtration efficiency is improved, preferably, the separation liquid is selected from glycol and/or water, and more preferably, the addition amount of the separation liquid is 40-120% of the mass of the Fischer-Tropsch wax.
Carbon deposition can be generated inside the catalyst pore channels when the waste MTP catalyst is subjected to MTP catalytic reaction, the number of the catalyst pore channels and the specific surface area are reduced, and the adsorption effect is reduced. According to the invention, in order to improve the adsorption effect of the adsorbent, under the preferable conditions, the method further comprises the step of pretreating the waste MTP catalyst, wherein the pretreatment comprises the following steps: the waste MTP catalyst is sequentially roasted, alkali soaked, acid soaked and crushed.
Further preferably, the roasting conditions at least satisfy: the temperature is 500-700 ℃, and the time is 3-8 h; preferably, the alkali soaking condition at least satisfies: the temperature is 80-100 ℃, and the soaking time is 5-12 h; more specifically, the alkali soaking comprises: soaking the calcined waste MTP catalyst in 0.1-2M alkali solution at 80-100 ℃ for 5-12h, wherein the kind of the alkali solution can be known by the technical personnel in the field, and can be potassium hydroxide solution and/or sodium hydroxide solution.
According to the invention, preferably, the acid soaking conditions at least satisfy: the soaking time is 5-12 h; more specifically, the acid soak comprises: soaking the waste MTP catalyst obtained by alkaline soaking in 0.1-2M acid solution for 5-12h, wherein the kind of the acid solution can be known by the technical personnel in the field, and can be at least one of hydrochloric acid, sulfuric acid and nitric acid.
According to the invention, in order to support and maintain a loose porous structure as much as possible by the clay adsorbent in the adsorbent A and improve the decolorization efficiency of the Fischer-Tropsch wax crude product, the particle size of the crushed waste MTP catalyst is preferably less than 50 meshes.
According to the invention, in step (2), the adsorbent can be made to sufficiently adsorb impurities in the fischer-tropsch wax on the one hand and sufficiently separate from the fischer-tropsch wax on the other hand, so as to facilitate the subsequent filtration, by aging, preferably under conditions at least: the temperature is 40-200 deg.C, and the time is 2-8 min. Wherein the pressure of the aging depends on the melting point of the Fischer-Tropsch wax and the boiling point of the separation liquid, and when the boiling point of the separation liquid is higher than the melting point of the Fischer-Tropsch wax, the aging can be carried out under normal pressure; when the boiling point of the separation liquid is lower than the melting point of the fischer-tropsch wax, the boiling point of the separation liquid is increased by increasing the aging pressure, which can be adjusted according to the actual operation, so long as the separation liquid can be maintained in a liquid state, in order to allow the separation liquid to exist in a liquid state in the molten fischer-tropsch wax.
According to the present invention, in order to further improve the decolorizing efficiency of fischer-tropsch wax, preferably under the conditions further comprising: and (3) circularly adding the refined Fischer-Tropsch wax into the crude Fischer-Tropsch wax in the step (1).
According to the invention, the method further comprises: and (3) recovering the separation liquid II, and circularly adding the separation liquid II into the mixed system in the step (2).
According to a particularly preferred embodiment of the present invention, the process for the decolorization of fischer-tropsch wax comprises:
(1) roasting the waste MTP catalyst for 3-8h at 500-700 ℃ in the air atmosphere, soaking in an alkali solution at 80-100 ℃ for 5-12h, then soaking in an acid solution for 5-12h, washing, drying, and then crushing to obtain waste MTP catalyst particles with the particle size of less than 50 meshes;
(2) adding an adsorbent A into the molten Fischer-Tropsch wax crude product, and performing first adsorption for 0-3h at the temperature of 40-200 ℃; adding an adsorbent B, and performing second adsorption at 40-200 ℃ for 0.2-2h to obtain a mixed system;
(3) under the condition of keeping the Fischer-Tropsch wax crude product in a molten state, adding a separation liquid I into the mixed system, and then aging and filtering to obtain refined Fischer-Tropsch wax, a separation liquid II and an adsorbent;
wherein the adsorbent A comprises clay;
the adsorbent B comprises, based on the total amount of the adsorbent B: 20-30 wt% of waste MTP catalyst, 10-20 wt% of clay, 20-40 wt% of activated carbon and 20-40 wt% of diatomite.
Based on the total amount of the adsorbent A and the adsorbent B, the content of the adsorbent A is 0-40 wt%, and the content of the adsorbent B is 60-100 wt%; the total amount of the adsorbent A and the adsorbent B is 0.5-10 wt% of the Fischer-Tropsch wax crude product.
The present invention will be described in detail below by way of examples. In the following examples, the spent MTP catalyst was a spent ZSM-5 catalyst from an olefin plant of Ningxia coal industries, the spent ZSM-5 catalyst comprising 79.5 wt% SiO217.7% by weight of Al2O30.4% by weight of Na2O, the carbon content of the spent ZSM-5 catalyst was 2.4 wt%, the physical parameters of the Fischer-Tropsch wax are shown in Table 1, and the composition of the adsorbent B is shown in Table 2.
TABLE 1
| Melting Point/. degree.C | Color number | |
| Fischer-Tropsch wax crude product A | 65 | 5 |
| Fischer-Tropsch wax crude product B | 105 | 7 |
TABLE 2
| Waste MTP | Clay | Activated carbon | Diatomite | |
| Adsorbent B1 | 25 | 15 | 30 | 30 |
| Adsorbent B2 | 40 | 0 | 35 | 25 |
| Adsorbent B3 | 60 | 20 | 0 | 20 |
| Adsorbent B4 | 50 | 0 | 50 | 0 |
| Adsorbent B5 | 20 | 80 | 0 | 0 |
(1) Pretreatment of waste MTP catalyst
Roasting the waste MTP catalyst at 550 ℃ for 4h in the air atmosphere, then soaking in a NaOH solution (1M) at 80 ℃ for 6h, washing and drying, then soaking in a hydrochloric acid solution (1M) for 6h, washing and drying, and then crushing to obtain waste MTP catalyst particles with the particle size of less than 50 meshes.
Example 1
Heating 150g of Fischer-Tropsch wax crude product A to 95 ℃ until the Fischer-Tropsch wax crude product A is completely melted, keeping the temperature of the Fischer-Tropsch wax crude product A at 75 ℃, adding argil, stirring and adsorbing for 1h, adding an adsorbent B1, stirring and adsorbing for 0.5h, and obtaining a mixed system;
150mL of distilled water at 70 ℃ was added to the mixed system while keeping the crude Fischer-Tropsch wax in a molten state, followed by aging for 3 hours to separate the layers of the mixed system, thereby obtaining a purified Fischer-Tropsch wax located in the upper layer of the distilled water and an adsorbent mixture located in the lower layer of the distilled water, which were then filtered to obtain an adsorbent mixture, 148g of a purified Fischer-Tropsch wax having a color number of 1, and water, respectively, and the results are shown in Table 3.
Example 2
The procedure of example 1 was followed except that adsorbent B2 was used in place of adsorbent B1, and the results are shown in Table 3.
Example 3
Heating 150g of Fischer-Tropsch wax crude product A to 95 ℃ until the Fischer-Tropsch wax crude product A is completely melted, keeping the temperature of the Fischer-Tropsch wax crude product A at 75 ℃, adding argil, stirring and adsorbing for 1h, adding an adsorbent B4, stirring and adsorbing for 0.5h, and obtaining a mixed system;
150mL of distilled water at 70 ℃ was added to the mixed system while keeping the crude Fischer-Tropsch wax in a molten state, followed by aging for 3 hours to separate the mixed system into layers, thereby obtaining a purified Fischer-Tropsch wax located in the upper layer of the distilled water and an adsorbent mixture located in the lower layer of the distilled water, which were then filtered to obtain an adsorbent mixture, 148g of a first purified Fischer-Tropsch wax having a color number of 2, and water, respectively, and the results are shown in Table 3.
Example 4
The procedure of example 3 was followed except that the adsorption was carried out without adding the adsorbent A, and the results are shown in Table 3.
Example 5
The first refined fischer-tropsch wax obtained in example 4 was refined again as follows:
132g of the first purified Fischer-Tropsch wax was heated to 95 ℃ until it was completely melted, the temperature of the crude Fischer-Tropsch wax A was maintained at 75 ℃, then, the adsorbent B3 was added to the mixture to conduct stirring and adsorption for 1 hour, 150mL of distilled water at 70 ℃ was added to the adsorbed sample, the mixture was allowed to stand for 4 hours to separate the mixed system, and a mixture of the purified Fischer-Tropsch wax on the upper layer of the distilled water and the adsorbent on the lower layer of the distilled water was obtained, and the mixture was filtered to obtain 130.8g of the second purified Fischer-Tropsch wax having color number 2, and the results are shown in Table 3.
Example 6
Heating 150g of Fischer-Tropsch wax crude product B to 140 ℃ to completely melt the sample, keeping the temperature of the sample at 115 ℃, adding argil to stir and adsorb for 1h, and adding adsorbent B5 to stir and adsorb for 1h to obtain a mixed system;
150mL of ethylene glycol at 115 ℃ was added to the mixed system while keeping the crude Fischer-Tropsch wax in a molten state, followed by aging for 3 hours to separate the mixed system into layers, thereby obtaining a purified Fischer-Tropsch wax located in the upper ethylene glycol layer and an adsorbent mixture located in the lower ethylene glycol layer, which were then filtered to obtain the adsorbent mixtures, and 148.2g of purified Fischer-Tropsch wax having a color number of 2 and ethylene glycol were separated, and the results are shown in Table 3.
Example 7
130g of the refined Fischer-Tropsch wax obtained in example 6 was heated to 140 ℃ until it was completely melted, the sample temperature was maintained at 115 ℃, and then clay was added thereto for stirring and adsorption for 1 hour, followed by addition of adsorbent B5 for stirring and adsorption for 1 hour.
150mL of ethylene glycol at 115 ℃ was added to the mixed system while keeping the crude Fischer-Tropsch wax in a molten state, followed by aging for 3 hours to separate the mixed system into layers, thereby obtaining a purified Fischer-Tropsch wax located in the upper ethylene glycol layer and an adsorbent mixture located in the lower ethylene glycol layer, which were then filtered to obtain an adsorbent mixture, 128.3g of a purified Fischer-Tropsch wax having a color number of 1, and ethylene glycol, respectively, and the results are shown in Table 3.
Comparative example 1
The process of example 3 was followed except that: the catalyst B consisted of diatomaceous earth and the results are shown in table 3.
Comparative example 2
The process of example 3 was followed except that: no pretreatment of the spent MTP catalyst was performed and the results are shown in table 3.
Comparative example 3
The process of example 4 was followed except that: the results are shown in Table 3 without addition of a separation liquid.
Test example
The Fischer-Tropsch wax color number is determined according to the petrochemical industry standard SH/T0403-92 of the people's republic of China, and the test results are shown in Table 2.
Yield of Fischer-Tropsch wax-weight of refined Fischer-Tropsch wax/weight of crude Fischer-Tropsch wax X100%
TABLE 3
As can be seen from the results in table 1, the decoloring efficiency of the fischer-tropsch wax can be improved by sequentially performing the first adsorption and the second adsorption on the fischer-tropsch wax crude product; by compounding the MTP catalyst with an adsorbent such as argil, the decolorizing efficiency and the yield of the Fischer-Tropsch wax can be remarkably improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A process for the decolorization of fischer-tropsch wax, comprising:
(1) adding an adsorbent A into the molten Fischer-Tropsch wax crude product for first adsorption; adding an adsorbent B for second adsorption to obtain a mixed system; or
Adding an adsorbent B into the molten Fischer-Tropsch wax crude product to directly perform second adsorption to obtain a mixed system;
(2) under the condition of keeping the Fischer-Tropsch wax crude product in a molten state, adding a separation liquid I into the mixed system, and then aging and filtering to obtain refined Fischer-Tropsch wax, a separation liquid II and an adsorbent;
wherein the adsorbent A comprises clay;
the adsorbent B comprises a spent MTP catalyst.
2. The process of claim 1, wherein the adsorbent B comprises a spent MTP catalyst, optionally clay, optionally activated carbon, and optionally diatomaceous earth;
preferably, the adsorbent B comprises, based on the total amount of the adsorbent B: 10-50 wt% of waste MTP catalyst, 0-80 wt% of clay, 0-90 wt% of active carbon and 0-50 wt% of diatomite.
3. The process of claim 1 or 2, wherein the adsorbent B comprises: 20-30 wt% of waste MTP catalyst, 10-20 wt% of clay, 20-40 wt% of activated carbon and 20-40 wt% of diatomite.
4. The method according to any one of claims 1 to 3, wherein the content of the adsorbent A is 0 to 40% by weight and the content of the adsorbent B is 60 to 100% by weight, based on the total amount of the adsorbent A and the adsorbent B;
preferably, the total amount of adsorbent a and adsorbent B used is 0.5-10 wt% of the crude fischer-tropsch wax.
5. The process of any of claims 1-4, wherein the spent MTP catalyst is a spent ZSM-5 catalyst;
preferably, the spent ZSM-5 catalyst has a pore size of
The specific surface area is 300-500m2/g；
Preferably, the spent ZSM-5 catalyst includes 75 to 90 wt% SiO based on the total amount of the spent ZSM-5 catalyst210-25% by weight of Al2O30-1% by weight of Na2O；
Preferably, the carbon content of the spent ZSM-5 catalyst is in the range of 0 to 10 wt%;
preferably, the separation liquid is selected from water and/or ethylene glycol.
6. The method of any of claims 1-5, further comprising pre-treating the spent MTP catalyst, the pre-treating comprising:
the waste MTP catalyst is sequentially roasted, alkali soaked, acid soaked and crushed.
7. The method of claim 6, wherein the firing conditions at least satisfy: the temperature is 500-700 ℃, and the time is 3-8 h;
preferably, the alkali soaking condition at least satisfies: the temperature is 80-100 ℃, and the soaking time is 5-12 h;
preferably, the acid soaking conditions at least satisfy: the soaking time is 5-12 h;
preferably, the particle size of the pulverized spent MTP catalyst is less than 50 mesh.
8. The method according to any one of claims 1 to 7, wherein in step (1), the conditions of the first adsorption are at least satisfied: the temperature is 40-200 ℃, and the time is 0-3 h;
preferably, the second adsorption condition at least satisfies: the temperature is 40-200 ℃, and the time is 0.2-2 h;
preferably, in step (2), the aging condition at least satisfies: the temperature is 40-200 deg.C, and the time is 2-8 min.
9. The method of any of claims 1-8, further comprising: and (3) circularly adding the refined Fischer-Tropsch wax into the crude Fischer-Tropsch wax in the step (1).
10. The method of any of claims 1-9, further comprising: and (3) recovering the separation liquid II, and circularly adding the separation liquid II into the mixed system in the step (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011604777.0A CN112852481B (en) | 2020-12-30 | 2020-12-30 | Method for decolorizing Fischer-Tropsch wax |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011604777.0A CN112852481B (en) | 2020-12-30 | 2020-12-30 | Method for decolorizing Fischer-Tropsch wax |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112852481A true CN112852481A (en) | 2021-05-28 |
| CN112852481B CN112852481B (en) | 2022-12-27 |
Family
ID=75998436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011604777.0A Active CN112852481B (en) | 2020-12-30 | 2020-12-30 | Method for decolorizing Fischer-Tropsch wax |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112852481B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1161367A (en) * | 1997-01-13 | 1997-10-08 | 中国石化大庆石油化工总厂研究院 | Method for refining petroleum wax by using compound adsorption agent |
| US20020052423A1 (en) * | 1999-09-21 | 2002-05-02 | Hydrocarbon Technologies, Inc. | Skeletal iron catalyst having improved attrition resistance and product selectivity in slurry-phase synthesis processes |
| CN107118849A (en) * | 2017-07-14 | 2017-09-01 | 河南华泰粮油机械股份有限公司 | The production method of refined rice bran wax |
| CN109485064A (en) * | 2018-12-10 | 2019-03-19 | 卓悦环保新材料（上海）有限公司 | The method of useless MTP catalyst preparation modenite and the application of useless MTP catalyst |
-
2020
- 2020-12-30 CN CN202011604777.0A patent/CN112852481B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1161367A (en) * | 1997-01-13 | 1997-10-08 | 中国石化大庆石油化工总厂研究院 | Method for refining petroleum wax by using compound adsorption agent |
| US20020052423A1 (en) * | 1999-09-21 | 2002-05-02 | Hydrocarbon Technologies, Inc. | Skeletal iron catalyst having improved attrition resistance and product selectivity in slurry-phase synthesis processes |
| CN107118849A (en) * | 2017-07-14 | 2017-09-01 | 河南华泰粮油机械股份有限公司 | The production method of refined rice bran wax |
| CN109485064A (en) * | 2018-12-10 | 2019-03-19 | 卓悦环保新材料（上海）有限公司 | The method of useless MTP catalyst preparation modenite and the application of useless MTP catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 杨世成等: "FCC废催化剂用于石蜡吸附精制过程的研究", 《天津化工》, vol. 18, no. 5, 30 September 2004 (2004-09-30), pages 45 - 47 * |
| 赵娜娜等: "废MTP催化剂对模拟废水中对二甲苯的吸附作用", 《净水技术》, vol. 39, no. 9, 25 September 2020 (2020-09-25), pages 114 - 120 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112852481B (en) | 2022-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101766322B1 (en) | Process for producing mesophase pitch by hydrogenation of high-temperature coal tar | |
| CN105175633B (en) | A kind of Combined stone oleoresin hydrotreating method and processing system | |
| JP4930741B2 (en) | Method for producing hydrogenated petroleum resin and hydrogenation catalyst used in the production method | |
| CN105481745A (en) | Method for removing benzo[alpha]pyrene in fat-soluble natural extract | |
| CN112852481B (en) | Method for decolorizing Fischer-Tropsch wax | |
| CN102558444B (en) | Method for preparing dicyclopentadiene hydrogenated petroleum resin | |
| CN102002131B (en) | Method for preparing high-quality hydrogenised C9 petroleum resin | |
| CN111187445A (en) | Method for recycling whole waste polyester bottles and application | |
| CN108102712A (en) | A kind of combined technical method of mixed raw material production needle coke | |
| CN106986888B (en) | The discoloration method of ketoxime type silane crosslinker | |
| CN112980484B (en) | Method for producing special marine heavy fuel oil by using coal tar as raw material | |
| WO2022194284A1 (en) | Activated carbon, preparation method therefor, and use thereof in grease | |
| CN113797908B (en) | Catalyst carrier material and preparation method and application thereof | |
| CN111378498B (en) | Production method of environment-friendly aromatic oil for tires | |
| CN107638889A (en) | A kind of useless hydrogenation catalyst regeneration method | |
| CN110938462B (en) | Method for removing solid particles of oil slurry by using heat treatment centrifugal sedimentation-electrostatic method | |
| CN111378502B (en) | Method for producing aromatic hydrocarbon solvent oil by hydrogenating C9 aromatic hydrocarbon fraction cracked by ethylene | |
| CN116410794A (en) | Refining method of high-melting-point crude paraffin | |
| CN112547080A (en) | Method for recycling supported hydrogenation catalyst | |
| CN111744560A (en) | Method for recovering hydrogenation catalyst | |
| CN108130129B (en) | Two-stage hydrotreating regeneration process for waste mineral oil and catalyst preparation method | |
| CN114195165A (en) | Composite carrier with step pore structure distribution and preparation method thereof | |
| CN113736509B (en) | Treatment method for hydrogenation residual oil of slag oil slurry bed | |
| CN115011377B (en) | Method for separating solid matters from catalytic cracking slurry oil | |
| CN110982116B (en) | Preparation method of environment-friendly migration-free reclaimed rubber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |