CN115672255A - Mercaptan removing agent and aviation kerosene deodorization method - Google Patents
Mercaptan removing agent and aviation kerosene deodorization method Download PDFInfo
- Publication number
- CN115672255A CN115672255A CN202110873098.1A CN202110873098A CN115672255A CN 115672255 A CN115672255 A CN 115672255A CN 202110873098 A CN202110873098 A CN 202110873098A CN 115672255 A CN115672255 A CN 115672255A
- Authority
- CN
- China
- Prior art keywords
- mercaptan
- manganese
- copper
- temperature
- removing agent
- 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.)
- Pending
Links
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000003350 kerosene Substances 0.000 title claims abstract description 39
- 238000004332 deodorization Methods 0.000 title abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 60
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052802 copper Inorganic materials 0.000 claims abstract description 51
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical group [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000002808 molecular sieve Substances 0.000 claims abstract description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 9
- 150000002697 manganese compounds Chemical class 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- 150000003573 thiols Chemical class 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 3
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000006477 desulfuration reaction Methods 0.000 abstract description 6
- 230000023556 desulfurization Effects 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- 239000011572 manganese Substances 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000001877 deodorizing effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- -1 mn) 7+ Chemical compound 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- WCMHZFHLWGFVCQ-UHFFFAOYSA-N [Ba].[Mn] Chemical compound [Ba].[Mn] WCMHZFHLWGFVCQ-UHFFFAOYSA-N 0.000 description 1
- HVCXHPPDIVVWOJ-UHFFFAOYSA-N [K].[Mn] Chemical compound [K].[Mn] HVCXHPPDIVVWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Abstract
The invention discloses a mercaptan removing agent, which comprises a carrier and an active component, wherein the carrier is a manganese oxide molecular sieve, and the active component is copper 2 The content of copper element in O form is not less than 20% of total copper element. The mercaptan removal agent provided by the invention realizes the purification of mercaptan by utilizing the special crystal structure of the active phase through a mode of combining adsorption and catalytic conversion, has the advantages of low cost, high desulfurization precision, high sulfur capacity and high one-way conversion rate, and has a good mercaptan removal effect. The mercaptan removing agent can directly remove the aviation kerosene at a lower temperatureThe mercaptan in the product achieves the aim of deodorization, and the product has the advantages of simple process, convenient operation and good popularization prospect.
Description
Technical Field
The invention relates to the field of adsorbents, and particularly relates to a mercaptan removing agent and application of the mercaptan removing agent in aviation kerosene deodorization.
Background
Aviation kerosene (also called jet fuel, hereinafter referred to as aviation kerosene) is one of the products with the most control indexes and the most strict quality requirements in petroleum products. There are two main methods for producing aviation kerosene: the heavy distillate oil is prepared by high-medium pressure hydrocracking, and the straight run aviation kerosene fraction is refined, wherein the yield of the straight run aviation kerosene fraction is the maximum. The specific gravity, the freezing point, the smoke point and the sulfur content of straight-run aviation kerosene fractions of main crude oil at home and abroad basically meet the index requirements of aviation kerosene products, but mercaptan sulfur is generally higher, so that aviation kerosene generates foul smell, unstable substances in aviation kerosene are easy to oxidize and superpose to generate colloidal substances and sediments, the stability is influenced, engine precision parts are corroded, and the sensitivity of aviation kerosene to additives (such as an antioxidant, a metal passivator and the like) is influenced. In order to reduce the content of mercaptan sulfur in the aviation kerosene to the index specified in the national standard not more than 20 mu g/g, the refining process mainly comprises two technologies, namely hydrogenation technology and non-hydrogenation technology. Generally, a non-noble metal hydrofining catalyst is generally adopted in a hydrofining process, but the reaction pressure, the temperature and the hydrogen-oil ratio are higher, so that the investment and the operation cost are also higher; or the use of noble metal catalyst can reduce the severity of operating conditions, but noble metal catalyst has high cost, is easy to compensate sulfide poisoning, and the operating cycle is affected. Therefore, the selective adsorption desulfurization technology is promising in the prospect of removing the mercaptan in the aviation kerosene, and has important significance for supporting the development of the national aviation industry and improving the production scale and economic benefit of the aviation kerosene for enterprises. The development of a mercaptan removal agent with high mercaptan capacity, low cost and simple operation has very practical significance.
Disclosure of Invention
The invention aims to provide a mercaptan removing agent and a method for deodorizing aviation kerosene, and in order to realize the aim, the invention specifically comprises the following two aspects:
the invention provides a mercaptan removing agent, which comprises a carrier and an active component, wherein the carrier is a manganese oxide molecular sieve, and the active component is copper 2 The content of copper element in O form is not less than 20% of total copper element.
The invention also provides a method for deodorizing aviation kerosene, which comprises the step of contacting the mercaptan removing agent with the aviation kerosene raw material containing the mercaptan in a closed reactor isolated from oxygen, wherein the contact conditions comprise that: the temperature is between room temperature and 100 ℃, and the time is between 0.1 and 12 hours. The room temperature of the invention refers to the environmental temperature which does not need to be heated, and is generally 13-35 ℃, that is, the temperature range of the contact condition of the invention can be 15-100 ℃, 20-100 ℃ and the like according to the difference of the environmental temperature.
The active component in the mercaptan removal agent provided by the invention is copper, and the active component is Cu 2 The O content is not less than 20 percent of the total copper element, the mercaptan purification is realized by utilizing the special crystal structure of the active phase through a mode of combining adsorption and catalytic conversion, the cost is low, the desulfurization precision is high, the sulfur capacity is high, the one-way conversion rate is high, and the mercaptan removal effect is good. The mercaptan removing agent can directly remove mercaptan in aviation kerosene at a lower temperature to achieve the aim of deodorization, and has the advantages of simple process, convenience in operation and good popularization prospect.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
The invention provides a mercaptan removing agent, which comprises a carrier and an active component, wherein the carrier is a manganese oxide molecular sieve, and the active component is copper 2 The content of copper element in the form of O is not less than 20%, preferably not less than 30%, more preferably 30 to 80% of the total copper element.
The carrier in the mercaptan removing agent is a manganese oxide molecular sieve, and the active component is a copper substance. The manganese oxide molecular sieve can be one or more of birnessite, bussel ore, birnessite, barium manganese ore, potassium manganese ore and manganite, and the copper part of the active component is Cu 2 Form OAre present. The content of each component in the mercaptan removal agent in the invention is preferably as follows based on the dry weight of the mercaptan removal agent: the content of the carrier is 80-99.5 wt%, and the content of the copper active component calculated by CuO is 0.5-20 wt%.
The specific surface area and pore volume of the mercaptan-removing agent of the present invention are not particularly limited, and generally, the specific surface area may be 50 to 300m 2 Per g, pore volume can be 0.2-1.2cm 3 /g。
The mercaptan removing agent used in the invention is not particularly limited in source, can be a commercial agent, and can also be prepared by raw materials, as long as the composition, the content and related parameters meet the corresponding requirements of the invention. In order to better implement the method of the invention, the invention provides two preparation methods for obtaining the mercaptan removal agent, namely a doping method and a loading method, which are respectively described as follows:
the method a is a doping method, which is to mix a reduced manganese compound with copper metal salt and then mix the reduced manganese compound with an oxidized manganese compound for hydrothermal reaction so as to avoid the copper metal salt and the oxidized manganese compound from forming an undesired complex compound to change the crystal structure, and mainly comprises the following steps:
(a-1) dissolving a reduced manganese compound and copper metal salt in water to obtain a mixed solution;
(a-2) mixing an oxidation state manganese compound with the mixed solution in the step (a-1), carrying out hydrothermal reaction, and collecting a precipitate;
(a-3) drying, roasting and activating the precipitate obtained in the step (a-2) to obtain the mercaptan removing agent.
The manganese compounds in the oxidized and reduced forms of the invention are relative; the manganese compound in an oxidized state is generally referred to as containing a relatively high valence state of manganese (e.g., mn) 7+ 、Mn 6+ Etc.), reduced manganese compounds generally refer to compounds containing relatively low levels of manganese (e.g., mn) 2+ Etc.). For example, the oxidation state manganese compound is selected from one or more of potassium permanganate, potassium manganate and sodium permanganate, the copper metal salt is selected from one or more of copper nitrate, copper sulfide and copper chloride, and the reduction state manganese compound is selected from one or more of copper nitrate, copper sulfide and copper chlorideOne or more of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride; preferably, the molar ratio of the oxidized manganese compound, the reduced manganese compound and the copper metal salt is (0.2 to 3): 1: (0.01-1).
And (3) washing the precipitate obtained in the step (a-2) according to needs, wherein the washing refers to washing the collected solid product by using deionized water until the washing liquid is neutral (for example, the pH value is 6.5-7.5).
The drying and calcination in the step (a-3) are conventional operations in the art, and the relevant conditions are not particularly limited, for example, the temperature of the drying in the step (a-3) is 80 to 350 ℃, preferably 100 to 300 ℃, and the time is 1 to 24 hours, preferably 2 to 12 hours; the roasting temperature is 200-900 ℃, preferably 250-800 ℃ and the time is 0.5-12 h, preferably 2-6 h. The calcination may be carried out in an air atmosphere or in an inert gas atmosphere, preferably N 2 The reaction is carried out in an atmosphere.
In order to further improve the performance of the mercaptan removal agent, between the step (a-2) and the step (a-2), the method also comprises the step of adding acid into the mixed solution, and adjusting the pH value of the mixed solution to 0.2-3; the acid may be common inorganic acid such as nitric acid, hydrochloric acid, sulfuric acid, etc., or organic acid such as acetic acid, etc. for achieving the above purpose.
The method b is a loading method, firstly preparing a manganese oxide molecular sieve from an oxidation state manganese compound and a reduction state manganese compound, and then loading copper metal salt on the manganese oxide molecular sieve, and specifically comprises the following steps:
(b-1) carrying out hydrothermal reaction on an aqueous solution containing an oxidized manganese compound and a reduced manganese compound, collecting a solid product, and carrying out first drying and first roasting to obtain a manganese oxide molecular sieve;
and (b-2) loading copper metal salt on the manganese oxide molecular sieve, performing second drying and second roasting, and then activating to obtain the mercaptan removing agent.
Wherein the selection and content of the oxidized manganese compound, the reduced manganese compound and the copper metal salt can be referred to method a, and the method preferably comprises the step of adding acid into the aqueous solution before the hydrothermal reaction is carried out, the pH value of the aqueous solution is adjusted to 0.2-3, and the selection of the type of the acid can also be referred to method a.
The hydrothermal reaction in the method b adopts the conventional conditions in the field, the temperature is usually controlled to be 80-200 ℃, and the hydrothermal reaction temperature can be adjusted to be 150-200 ℃ in the method a, so that the manganese oxide molecular sieve crystal structure is formed, and copper-manganese ore (CuMn) is also formed at the same time 2 O 4 )。
The purpose of the activation in step (a-3) and step (b-2) is to convert part or all of the copper present in the form of CuO therein to Cu 2 O form, preferably said activation conditions comprise: the activating atmosphere is a reducing gas atmosphere, wherein the reducing gas is hydrogen and/or carbon monoxide, the balance is nitrogen and/or inert gas, the volume content of the reducing gas is 1-50%, more preferably 2-30%, the activating temperature is 50-200 ℃, more preferably 80-180 ℃, and the activating time is 0.5-5 hours, more preferably 0.8-3 hours.
The invention also provides a method for deodorizing aviation kerosene, which comprises the step of contacting the mercaptan removing agent with the aviation kerosene raw material containing the mercaptan in a reactor isolated from oxygen, wherein the contact conditions comprise that: the temperature is between room temperature and 100 ℃, and the time is between 0.1 and 12 hours.
The source, the type and the content of the mercaptan-containing aviation kerosene raw material are not particularly limited, and the aviation kerosene which needs to be deodorized can be treated by the mercaptan removing agent provided by the invention so as to achieve the aim of deodorization. For example, aviation kerosene is produced by subjecting heavy distillate to high-medium pressure hydrocracking, aviation kerosene is produced by refining straight-run aviation kerosene fraction, and the like.
According to the method, the deodorization of the aviation kerosene is carried out in an oxygen-isolated reactor, which can be a closed reactor protected by nitrogen and/or inert gas and can also be a continuous reaction under the atmosphere of nitrogen and/or inert gas. In the contact process, the contact efficiency can be increased by various conventional modes, and the deodorization effect is improved.
The method provided by the invention can directly obtain the aviation kerosene with ultralow mercaptan content at a lower temperature, the mercaptan removal agent has low cost, high mercaptan removal precision, high sulfur capacity and high one-way conversion rate, and the deodorization method has the advantages of convenient process and simple operation, and is beneficial to industrial popularization.
The present invention is further illustrated by the following specific examples, which describe preferred embodiments, but which are not to be construed as limiting the invention, and any person skilled in the art may, by applying the above teachings, modify the equivalent embodiments equally.
Reagents, instruments and tests
Unless otherwise specified, all reagents used in the invention are analytically pure, and all reagents are commercially available.
The model of the XRD diffractometer adopted by the invention is an XRD-6000X-ray powder diffractometer (Shimadzu Japan), and the XRD test conditions are as follows: cu target, K α ray (wavelength λ =0.154 nm), tube voltage 40kV, tube current 200mA, scanning speed 10 ° (2 θ)/min.
The content of the active component was measured by X-ray fluorescence spectroscopic analysis RIPP 132-90 (petrochemical analysis (RIPP test method), yang Cuiding, gu Kanying, wu Wenhui eds., scientific Press, first edition 9.1990, p.371-379).
H used in the invention 2 The S analyzer was a German SICK GMS810 hydrogen sulfide analyzer.
Example 1
Dissolving 3.17g of potassium permanganate in 40.55g of deionized water, heating and stirring to dissolve the potassium permanganate to form a potassium permanganate solution, mixing 5.78g of 50 wt% manganese sulfate solution and 1.22g of copper nitrate, uniformly stirring, mixing the two solutions, adding 6ml of nitric acid, uniformly stirring, adjusting the pH value to be less than 3, and reacting at 130 ℃ for 24 hours. Filtering the brown precipitate, washing with deionized water for several times until the pH of the washing solution =7, drying the solid product at 120 deg.C overnight and calcining at 400 deg.C for 4h, and then at 10% H 2 Heating to 120 ℃ in an-Ar atmosphere for treatment for 1h to prepare a mercaptan removing agent A1:3% of CuO-OMS-2, wherein, with Cu 2 The copper element in the form of O accounts for 58 percent of the total copper element.
Example 2
Mercaptan-removing agent A2 was prepared by the same procedure as in example 1, except thatThe active component CuO is selected to have different content, and the composition of A2 is 6 percent of CuO-OMS-2, wherein, cu is used 2 The copper element in the O form accounts for 48 percent of the total copper element.
Example 3
A mercaptan-removing agent A3 was prepared by the same procedure as in example 1, except that the hydrothermal reaction temperature was not uniform, and the hydrothermal reaction was carried out at 190 ℃ to obtain a mercaptan-removing agent A3:3% of CuO-OMS-2-190, wherein, with Cu 2 The copper element in the O form accounts for 37 percent of the total copper element.
Example 4
Mixing the potassium permanganate solution with the manganese sulfate solution, copper nitrate and nitric acid, transferring the mixture to a flask provided with a condenser tube, refluxing the mixture at 120 ℃ for 24 hours, and obtaining a mercaptan removing agent A4 by the steps which are the same as those in the example 1:3% of CuO-OMS-2-Ref, wherein, cu 2 The copper element in the O form accounts for 40 percent of the total copper element.
Example 5
Firstly, preparing a manganese molecular sieve OMS-2 carrier by a hydrothermal synthesis method, dissolving 3.17g of potassium permanganate in 40.55g of deionized water, heating and stirring to dissolve the potassium permanganate to form a potassium permanganate solution, then mixing the potassium permanganate solution with 5.78g of 50 wt% manganese sulfate solution, adding 6ml of nitric acid to adjust the pH value of the solution to 1.0, stirring uniformly, and reacting at 130 ℃ for 24 hours. The resulting brown precipitate was filtered and washed several times with deionized water until the pH of the washing solution =7, and then the solid product was dried at 120 ℃ overnight, followed by calcination at 400 ℃ for 4h in an air atmosphere to prepare manganese oxide molecular sieve OMS-2.
Then, copper nitrate was supported on an OMS-2 carrier by a supporting method, and after drying the solid product at 120 ℃ overnight and calcining it in air at 500 ℃ for 4 hours, the solid product was activated by the activation method in example 1 to obtain a thiol remover A6:15% of CuO-OMS-2, wherein, cu 2 The copper element in the O form accounts for 29 percent of the total copper element.
Comparative example 1
Commercial zinc oxide desulfurizing agent (hereinafter referred to as D1) was selected as the mercaptan-removing agent.
XRD analysis of the mercaptan-removing agent obtained in the example shows only characteristic peak of OMS-2, which shows that the mercaptan-removing agent has OMS-2 molecular sieve structure and active component copper is uniformly doped. The substitution of the doping method for the loading method does not affect the crystal properties of the thiol remover.
Example 6
0.5g of the mercaptan removal agent A1 of example 1 was transferred to a 50g reaction kettle containing mercaptan industrial aviation kerosene distillate oil under the condition of oxygen isolation, the reaction kettle was filled with nitrogen, stirred and reacted for 1 hour at 50 ℃ under normal pressure, the mercaptan removal agent was removed by filtration after the reaction kettle was cooled to room temperature, and an oil sample was taken out for analysis of mercaptan content, and the results are shown in Table 1.
Examples 7 to 10
The aviation kerosene fraction was treated in the same manner as in test example 6 except that the mercaptan-removing agents were A2 to A5, respectively, and the results are shown in Table 1.
Example 8
The aviation kerosene fraction was treated in the same manner as in example 6 except that the mercaptan-removing agent A3 was selected for the desulfurization of the aviation kerosene fraction, and the results are shown in Table 1.
Comparative example 2
Comparative example D1 was selected for the mercaptan removal reaction with the aviation kerosene fraction in the same manner as in example 6, and the results are shown in Table 1.
TABLE 1
*“Cu 2 O ratio "represents Cu in the mercaptan-removing agent 2 The form of O contains copper element in percentage of total copper element.
According to the physicochemical properties of the manganese molecular sieve, the invention fully utilizes the special crystal structure of the copper-based-manganese molecular sieve to fully exert the advantages of the copper-based-manganese molecular sieve in the field of mercaptan removal, so that the copper-based-manganese molecular sieve can have high mercaptan removal performance at a lower temperature. As shown in Table 1, in the mercaptan removal agent provided by the invention, cu is used as an active component after the copper-based molecular sieve adsorbent is subjected to activation treatment 2 The percentage of copper element existing in O form in the total copper element is higher than 20%, and the copper-manganese ore crystal formed in the structure of the mercaptan removing agent can be further increasedThe desulfurization precision is improved, so that the mercaptan removal performance is greatly improved. In addition, the specific surface area and the pore volume of the mercaptan removal agent are obviously larger than those of the comparative zinc oxide, so that the pore volume and the specific surface area of the mercaptan removal agent are increased, mercaptan molecules can enter pore channels of the mercaptan removal agent, and the mercaptan removal agent are promoted to be adsorbed. Therefore, the desulfurization precision of the mercaptan removing agent provided by the invention is obviously higher than that of the prior art comprising a commercial zinc oxide desulfurizing agent when the mercaptan removing agent is used for mercaptan removing reaction including aviation kerosene deodorization. The mercaptan removing agent disclosed by the invention is simple in preparation mode, good in repeatability and beneficial to industrial popularization.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.
Claims (12)
1. A mercaptan removing agent comprises a carrier and an active component, wherein the carrier is a manganese oxide molecular sieve, and the active component is copper, and is characterized in that the active component contains Cu 2 The content of copper element in O form is not less than 20% of total copper element.
2. The thiol remover according to claim 1, wherein the manganese oxide molecular sieve is selected from one or more of birnessite, buchner, birnessite, bartonite, kalmanesite, and cadusate.
3. The thiol remover according to claim 1, characterized in that the carrier is present in an amount of 80-99.5 wt.%, and the active component, calculated as CuO, is present in an amount of 0.5-20 wt.%, based on the dry weight of the thiol remover.
4. The mercaptan-removal agent as defined in claim 1, wherein Cu is selected as the active component 2 The content of copper element in O form is not less than 30% of total copper element.
5. The mercaptan removal agent according to claim 1, wherein the mercaptan removal agent is prepared by the method a or the method b;
the method a comprises the following steps:
(a-1) dissolving a reduced manganese compound and copper metal salt in water to obtain a mixed solution;
(a-2) mixing an oxidation state manganese compound with the mixed solution in the step (a-1), carrying out hydrothermal reaction, and collecting a precipitate;
(a-3) drying, roasting and activating the precipitate obtained in the step (a-2) to obtain the mercaptan removing agent;
the method b comprises the following steps:
(b-1) carrying out hydrothermal reaction on an aqueous solution containing an oxidized manganese compound and a reduced manganese compound, collecting a solid product, and carrying out first drying and first roasting to obtain a manganese oxide molecular sieve;
and (b-2) loading copper metal salt on the manganese oxide molecular sieve, performing second drying and second roasting, and then activating to obtain the mercaptan removing agent.
6. The mercaptan removal agent as defined in claim 5, wherein in method a and method b, the manganese compounds in an oxidized state are respectively and independently selected from one or more of potassium permanganate, potassium permanganate and sodium permanganate, the copper metal salts are respectively and independently selected from one or more of copper nitrate, copper sulfide and copper chloride, and the manganese compounds in a reduced state are respectively and independently selected from one or more of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride;
preferably, the molar ratio of the oxidized manganese compound, the reduced manganese compound and the copper metal salt is (0.2-3): 1: (0.01-1).
7. The mercaptan removal agent as defined in claim 5, wherein in the step (a-3) of the method a, the drying temperature is 80-350 ℃, the drying time is 1-24 hours, the roasting temperature is 200-900 ℃, and the drying time is 0.5-12 hours; in the method b, the temperature of the first drying is 80-350 ℃, the time is 1-24 h, the temperature of the first roasting is 200-900 ℃, the time is 0.5-12 h, the temperature of the second drying is 80-350 ℃, the time is 1-24 h, and the temperature of the second roasting is 200-900 ℃, and the time is 0.5-12 h.
8. The mercaptan-removing agent according to claim 5, wherein the pH of the mixed solution is adjusted to 0.2-3 by adding an acid to the mixed solution between the steps (a-2) and (a-2).
9. The mercaptan removal agent as defined in claim 5, further comprising a step of adding an acid to the aqueous solution to adjust the pH of the aqueous solution to 0.2-3, prior to the hydrothermal reaction in the step b.
10. The mercaptan removal agent according to claim 5, wherein said activation conditions in Process a and/or Process b comprise: the activation atmosphere is a reducing gas atmosphere, wherein the reducing gas is H 2 And/or CO, the volume content of the reducing gas is 1-50%, preferably 2-30%, the activation temperature is 50-200 ℃, preferably 80-180 ℃, and the activation time is 0.5-5 hours, preferably 0.8-3 hours.
11. A process for deodorising aviation kerosene comprising contacting a mercaptan-removing agent with a feed stock comprising mercaptan aviation kerosene in an oxygen-depleted reactor under conditions comprising: the temperature is between room temperature and 100 ℃, and the time is between 0.1 and 12 hours; characterized in that the mercaptan removal agent is according to any one of claims 1-10.
12. The method of claim 11, wherein the mercaptan content of the mercaptan-containing aviation kerosene feedstock is in the range of 20ppm to 120ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110873098.1A CN115672255A (en) | 2021-07-30 | 2021-07-30 | Mercaptan removing agent and aviation kerosene deodorization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110873098.1A CN115672255A (en) | 2021-07-30 | 2021-07-30 | Mercaptan removing agent and aviation kerosene deodorization method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115672255A true CN115672255A (en) | 2023-02-03 |
Family
ID=85059223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110873098.1A Pending CN115672255A (en) | 2021-07-30 | 2021-07-30 | Mercaptan removing agent and aviation kerosene deodorization method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115672255A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712590A (en) * | 2008-09-18 | 2010-05-26 | 罗门哈斯公司 | Improved process for the oxidative dehydrogenation of ethane |
| US20160175806A1 (en) * | 2014-12-17 | 2016-06-23 | University Of Connecticut | Adsorptive desulfurization |
| CN112791721A (en) * | 2019-10-28 | 2021-05-14 | 中国石油化工股份有限公司 | Supported catalyst precursor, supported catalyst, preparation method and activation method |
-
2021
- 2021-07-30 CN CN202110873098.1A patent/CN115672255A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712590A (en) * | 2008-09-18 | 2010-05-26 | 罗门哈斯公司 | Improved process for the oxidative dehydrogenation of ethane |
| US20160175806A1 (en) * | 2014-12-17 | 2016-06-23 | University Of Connecticut | Adsorptive desulfurization |
| CN112791721A (en) * | 2019-10-28 | 2021-05-14 | 中国石油化工股份有限公司 | Supported catalyst precursor, supported catalyst, preparation method and activation method |
Non-Patent Citations (1)
| Title |
|---|
| YU HUANG ET AL.: "Highly Efficient and Recyclable Fe-OMS-2 Catalyst for Enhanced Degradation of Acid Orange 7in Aqueous Solution", 《CHEMISTRY SELECT》, vol. 5, pages 3272 - 3277 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111215084A (en) | Copper-based catalyst for preparing methanol by carbon dioxide hydrogenation, preparation and application thereof | |
| WO2023231474A1 (en) | Catalyst for preparing olefins by dehydrogenation of light alkane and application thereof | |
| Zhang et al. | Microwave-assisted rapid synthesis of bismuth molybdate with enhanced oxidative desulfurization activity | |
| CN110496618B (en) | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation | |
| CN114345329A (en) | Application of normal-pressure ultra-deep desulfurization catalyst | |
| CN111250096A (en) | Non-noble metal isobutane dehydrogenation catalyst with hexagonal mesoporous material as carrier and preparation method and application thereof | |
| CN115672255A (en) | Mercaptan removing agent and aviation kerosene deodorization method | |
| CN111375375B (en) | Desulfurization adsorbent and preparation method thereof | |
| CN113522347B (en) | Sweetening catalyst, preparation method thereof and sweetening method | |
| CN111135852A (en) | Non-noble metal isobutane dehydrogenation catalyst with rodlike mesoporous molecular sieve as carrier and preparation method and application thereof | |
| CN102441388B (en) | Preparation method for cobalt-base Fischer Tropsch synthetic catalyst with high stability | |
| CN112569988B (en) | Composition containing precipitated epsilon/epsilon' iron carbide and theta iron carbide, preparation method, catalyst, application and Fischer-Tropsch synthesis method | |
| CN113522302B (en) | Hydrogen sulfide remover and preparation method and application thereof | |
| CN110479323B (en) | Catalyst for preparing CO by reverse water-gas conversion method and preparation method thereof | |
| CN104588108B (en) | Heavy-oil hydrogenation catalyst and its preparation method and application | |
| CN115678592A (en) | Method for removing mercaptan in gasoline at lower temperature | |
| JPH07171390A (en) | Catalyst based on highly dispersed metal oxide particularly containing zirconia | |
| CN112569993A (en) | Supported epsilon/epsilon' iron carbide-containing composition, preparation method thereof, catalyst and application thereof, and Fischer-Tropsch synthesis method | |
| CN111569938A (en) | Hydrofining catalyst and preparation method and application thereof | |
| CN111250097A (en) | Non-noble metal isobutane dehydrogenation catalyst with spherical mesoporous silica as carrier and preparation method and application thereof | |
| CN115678629A (en) | Method for producing liquefied gas with ultra-low sulfur content | |
| CN113522348B (en) | Hydrogen sulfide remover and preparation method and application thereof | |
| CN102441389B (en) | Preparation method of cobalt-based catalyst for Fischer Tropsch synthesis | |
| Liu et al. | Single-source approach to amorphous RuS2 materials supported on SBA-15 and their catalytic activity for thiophene hydrodesulfurization | |
| CN115678590A (en) | Pretreatment method of sulfur-carbon-containing four-raw oil for alkylation |
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 |