CN115678629A - Method for producing liquefied gas with ultra-low sulfur content - Google Patents
Method for producing liquefied gas with ultra-low sulfur content Download PDFInfo
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- CN115678629A CN115678629A CN202110869551.1A CN202110869551A CN115678629A CN 115678629 A CN115678629 A CN 115678629A CN 202110869551 A CN202110869551 A CN 202110869551A CN 115678629 A CN115678629 A CN 115678629A
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- desulfurization adsorbent
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 53
- 239000011593 sulfur Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 58
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 52
- 230000023556 desulfurization Effects 0.000 claims abstract description 52
- 239000003463 adsorbent Substances 0.000 claims abstract description 43
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical group [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 36
- 239000002808 molecular sieve Substances 0.000 claims abstract description 19
- 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 19
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- 150000002697 manganese compounds Chemical class 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 13
- 239000012286 potassium permanganate Substances 0.000 claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 239000012265 solid product Substances 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 7
- 239000002244 precipitate 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
- 238000011068 loading method Methods 0.000 claims description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- 239000011702 manganese sulphate Substances 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
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 150000003568 thioethers Chemical class 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
- 229910021578 Iron(III) chloride Inorganic materials 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
- 229960002413 ferric citrate Drugs 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 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 10
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000012298 atmosphere Substances 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
- 230000000694 effects Effects 0.000 description 5
- 229910052742 iron Inorganic materials 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000003915 liquefied petroleum gas Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- -1 mn7+ Chemical compound 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 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
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZRVUJXDFFKFLMG-UHFFFAOYSA-N Meloxicam Chemical compound OC=1C2=CC=CC=C2S(=O)(=O)N(C)C=1C(=O)NC1=NC=C(C)S1 ZRVUJXDFFKFLMG-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CJDZJALAGKVFOV-UHFFFAOYSA-N [K+].[K+].[O-][Mn]([O-])=O Chemical compound [K+].[K+].[O-][Mn]([O-])=O CJDZJALAGKVFOV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WBYBBYXHPDBWJL-UHFFFAOYSA-N barium(2+);dioxido(oxo)manganese Chemical compound [Ba+2].[O-][Mn]([O-])=O WBYBBYXHPDBWJL-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012994 industrial processing Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for producing liquefied gas with ultra-low sulfur content, which comprises the following steps of contacting a desulfurization adsorbent with a liquefied gas raw material containing sulfur, wherein the contacting conditions comprise that: the temperature is normal temperature to 200 ℃, and the volume space velocity is 500 to 20000h ‑1 (ii) a The desulfurization adsorbent contains a carrier and an active component, wherein the carrier is a manganese oxide molecular sieve, and the active component is iron oxide. The method can remove sulfur-containing substances in the sulfur-containing liquefied gas at normal temperature or lower temperature, and the purification of the sulfur-containing substances is realized by utilizing the special crystal structure of the active phase and combining the adsorption with the catalytic conversion, so that the liquefied gas with ultra-low sulfur content is obtained. The desulfurization adsorbent used in the invention has low cost and high desulfurization precisionThe method has the advantages of high sulfur capacity, high single-pass conversion rate, convenient operation of the production method, simple process and contribution to industrial popularization.
Description
Technical Field
The invention relates to the field of industrial gas treatment, in particular to a method for producing liquefied gas with ultra-low sulfur content.
Background
Along with the height of the inletThe increase of the processing amount of the sulfur crude oil and the blending proportion of the residual oil, the sulfur content of liquefied gas produced by a catalytic cracking unit of a refinery is increased, and the liquefied gas usually contains H 2 S、COS、CS 2 Toxic and harmful components such as mercaptan, thioether and disulfide greatly affect subsequent industrial processing, civil fuel and the like, so that the liquefied gas must be subjected to deep desulfurization. The sweetening process in liquefied gas mainly adopts Merox extraction oxidation sweetening technology, fiber membrane process, fixed bed alkali-free sweetening process or adsorption method developed by UOP company in America. The alkali liquor consumption of the alkali washing process is large, and environmental pollution is easily caused; the catalyst of the Merox extraction oxidation process is easy to aggregate and deactivate, and the total desulfurization rate is not high; the fiber membrane mercaptan removal process has large investment and is easy to block impurities; the fixed bed adsorption process has high use temperature and high energy consumption.
The U.S. Pat. Nos. 4705620 and 2921020, and the domestic CN1990828A, etc. adopt new technology to improve the separation technology of the mixture of disulfide and the alkali liquor, reduce the content of disulfide in the alkali liquor, and improve the desulfurization rate of liquefied petroleum gas. The conventional melox method still has the following problems: (1) The cobalt phthalocyanine catalyst used is in an alkaline phase and is easy to aggregate and deactivate, so that the catalyst is frequently replaced and the cost of the catalyst is quite high; (2) The desulfurization rate is not stable enough, mainly because the concentration of disulfide in the regenerated alkali liquor is difficult to control, the alkali liquor brings the disulfide into the liquefied petroleum gas again, and the total desulfurization rate is reduced; (3) A large amount of alkaline waste residues are generated, and the damage to the surrounding environment is caused. The Merichem company in the United states adopts a fiber membrane contactor technology to promote the mass transfer rate between an alkali liquor phase and a hydrocarbon phase to be greatly improved, thereby improving the utilization rate of the alkali liquor, reducing the consumption of the alkali liquor and reducing the discharge of alkali residues (USP 4124494 and USP 4159964). But the removal rate of mercaptan by the fiber membrane desulfurization process is still influenced by the regeneration quality of alkali liquor, and the improvement of the total sulfur removal rate is not obvious; in addition, the method still generates a certain amount of alkaline residue, which causes pollution to the environment; finally, the process requires high purity of the various media, requires the installation of corresponding filters, and requires periodic cleaning, which increases maintenance costs.
The adsorption desulfurization technique is another commonly used method for removing organic sulfur in liquefied petroleum gas, and the method separates sulfides from the liquefied petroleum gas by utilizing the effects of physical adsorption, van der waals force, chemical adsorption, complex adsorption and the like formed between an adsorbent and the sulfides, and has the characteristics of simple and convenient operation, low investment and no pollution. Compared with a simple hydrodesulfurization method, the method can not cause octane number loss.
Disclosure of Invention
The invention aims to provide a method for producing liquefied gas with ultra-low sulfur content at normal temperature and low temperature by adopting a high-precision and high-sulfur-capacity desulfurization adsorbent. In order to achieve the above object, the present invention specifically includes the following:
the invention provides a method for producing liquefied gas with ultra-low sulfur content, which comprises the step of contacting a desulfurization adsorbent with a liquefied gas raw material containing sulfur, wherein the contacting conditions comprise that: the temperature is normal temperature to 200 ℃, and the volume space velocity is 500 to 20000h -1 (ii) a The desulfurization adsorbent contains a carrier and an active component, wherein the carrier is a manganese oxide molecular sieve, and the active component is iron oxide.
The method can remove the sulfur-containing substances in the sulfur-containing liquefied gas at normal temperature or lower temperature, and the purification of the sulfur-containing substances is realized by utilizing the special crystal structure of the active phase through a mode of combining adsorption with catalytic conversion, so that the liquefied gas with ultra-low sulfur content is obtained. The desulfurization adsorbent used in the invention has the advantages of low cost, high desulfurization precision, high sulfur capacity, high single-pass conversion rate, convenient operation of the production method, simple process and contribution to industrial popularization.
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 sulfur content of the ultra-low sulfur content liquefied gas is generally the mass content calculated by sulfur element, and generally the mass percentage or ppm is taken as a metering unit, the sulfur content of the ultra-low sulfur content liquefied gas is far lower than the sulfur content required by subsequent use or process, and generally the sulfur content of the ultra-low sulfur content liquefied gas obtained by the method is 1ppm.
The invention provides a method for producing liquefied gas with ultra-low sulfur content, which comprises the step of contacting a desulfurization adsorbent with a liquefied gas raw material containing sulfur, wherein the contacting conditions comprise that: the temperature is normal temperature to 200 ℃, and the volume space velocity is 500 to 20000h -1 (ii) a The contact conditions are preferably: the temperature is normal temperature to 150 ℃, and the volume space velocity is 800 to 10000h -1 (ii) a The desulfurization adsorbent contains a carrier and an active component, wherein the carrier is a manganese oxide molecular sieve, and the active component is iron oxide. The normal 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 15-200 ℃, 20-200 ℃ and the like according to the difference of the environmental temperature.
The source, the type of the sulfur-containing substances and the sulfur content of the raw oil of the sulfur-containing liquefied gas are not particularly limited, for example, the sulfur-containing liquefied gas can be liquefied gas produced by a catalytic cracking unit of a refinery, wherein the sulfur-containing substances are generally one or more of hydrogen sulfide, mercaptan, disulfide, carbonyl sulfide and thioether, and the content of the sulfur-containing substances is generally 10-200ppm.
The place where the desulfurization adsorbent is contacted with the liquefied sulfur-containing gas raw material according to the present invention is not particularly limited, and may be various types of reactors well known to those skilled in the art, preferably a fixed bed reactor, so that the liquefied sulfur-containing gas raw material gas is continuously passed through. In the contact process, the contact efficiency can be increased through various conventional modes, and the adsorption reaction effect is improved.
The carrier in the desulfurization adsorbent is a manganese oxide molecular sieve, and the active component is iron oxide. Wherein the manganese oxide molecular sieve can be selected from one or more of birnessite, bussel ore, birnessite, barium manganite, potassium manganite and manganositeThe iron oxide active component can be ferrous oxide (FeO) or ferric oxide (Fe) 2 O 3 ) Ferroferric oxide (Fe) 3 O 4 ) In one or more of the above-mentioned forms. Based on the dry weight of the desulfurization adsorbent, the content of each component in the desulfurization adsorbent in the invention is preferably as follows: the content of the carrier is 80-99.5 wt%, calculated as Fe 2 O 3 The iron oxide content is 0.5-20 wt%.
The specific surface area and pore volume of the desulfurization adsorbent of the present invention are not particularly limited, and generally, the specific surface area may be 50 to 300m 2 Per g, pore volume of 0.2-1.2m 3 /g。
The desulfurization adsorbent used in the invention is not particularly limited in source, can be a commercial reagent, and can also be prepared by the raw materials, as long as the composition and the content meet the corresponding requirements of the invention. In order to better realize the method of the invention, the invention provides two preparation methods for obtaining the desulfurization adsorbent, 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 an iron metal salt and then mix the reduced manganese compound with an oxidized manganese compound for hydrothermal reaction so as to avoid the iron 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 iron 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 and roasting the precipitate obtained in the step (a-2) to obtain the desulfurization adsorbent.
The manganese compounds in the oxidized and reduced form are relative terms in the present invention; an oxidized manganese compound generally refers to a compound containing a relatively high valence of manganese (e.g., mn7+, mn6+, etc.), and a reduced manganese compound generally refers to a compound containing a relatively low valence of manganese (e.g., mn2+, etc.). For example, the oxidized manganese compound is selected from one or more of potassium permanganate, potassium permanganate and sodium permanganate, the iron metal salt is selected from one or more of ferric nitrate, ferric sulfide, ferric chloride, ferric citrate and ferric acetate, and the reduced manganese compound is 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 iron 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 And the reaction is carried out under an atmosphere.
In order to further improve the performance of the desulfurization adsorbent, between the step (a-2) and the step (a-2), the method further 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 the manganese oxide molecular sieve from the oxidation state manganese compound and the reduction state manganese compound, and then loading the iron 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 iron metal salt on the manganese oxide molecular sieve, and performing second drying and second roasting to obtain the desulfurization adsorbent.
Wherein the selection and content of the oxidized manganese compound, the reduced manganese compound and the iron metal salt can be referred to method a, and the method preferably comprises the step of adding an acid to the aqueous solution before the hydrothermal reaction is carried out, and adjusting the pH value of the aqueous solution to 0.2-3, and the selection of the type of the acid can also be referred to method a.
The method provided by the invention can directly obtain the liquefied gas with ultra-low sulfur content at a lower temperature, and the desulfurization adsorbent has the advantages of low cost, high desulfurization precision, high sulfur capacity, high single-pass conversion rate, 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, ka radiation (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 spectrometry RIPP 132-90 (petrochemical analysis (RIPP test method), yang Cuiding, gu Kanying, wu Wenhui eds., scientific Press, first 9 th edition 1990, p. 371-379).
H used in the invention 2 The S analyzer was a German SICK GMS810 hydrogen sulfide analyzer.
Preparation 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 1.56g of ferric 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 to reach the pH of the washing liquid =7, then drying the solid product at 120 ℃ overnight and roasting the dried solid product in air at 500 ℃ for 4h to prepare the desulfurization adsorbent A1:10% of Fe 2 O 3 -OMS-2。
Preparation example 2
A desulfurization adsorbent A2 was prepared in the same manner as in preparation example 1, except that Fe as an active component was used 2 O 3 In a content of 15% Fe 2 O 3 -OMS-2。
Preparation example 3
The same procedure as in preparation example 1 was used to prepare a desulfurization adsorbent A3, except that the calcination atmosphere of the solid product was not uniform, and calcination in a nitrogen atmosphere was selected to obtain a desulfurization adsorbent A3:15% of Fe 2 O 3 -OMS-2N。
Preparation example 4
Mixing the potassium permanganate solution with the manganese sulfate solution, ferric nitrate and nitric acid, transferring the mixture into a flask with a condenser tube, refluxing the mixture at 120 ℃ for 24 hours, and obtaining a desulfurization adsorbent A4 by the steps which are the same as those in the example 1:10% of Fe 2 O 3 -OMS-2-Ref。
Preparation 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 loading ferric nitrate to an OMS-2 carrier, drying the solid product at 120 ℃ overnight, and roasting the dried solid product in air at 500 ℃ for 4 hours to obtain a desulfurization adsorbent A5:15% of Fe 2 O 3 -OMS-2。
Preparation of comparative example 1:
the desulfurization adsorbent is selected from commercial iron oxide desulfurizer (Shandong Maoyujia environmental protection HT506 type iron oxide desulfurizer, hereinafter referred to as D1).
XRD analysis is carried out on the desulfurization adsorbents of the preparation examples and the comparative example, and the preparation examples only show a characteristic peak of OMS-2, which shows that the desulfurization adsorbents have an OMS-2 molecular sieve structure and active metal iron is uniformly doped. When the roasting atmosphere is changed to N 2 When Mn is found in the crystals of the desulfurizing adsorbent A3 3 O 4 At this time, more oxygen vacancies are generated in the desulfurization adsorbent crystal, which is beneficial to increasing the sulfur capacity of the adsorbent.
Examples
The scheme and the effect for explaining the invention and the prior art in detail are as follows: weighing 1.5g of desulfurization adsorbent (or contrast agent), placing in a fixed bed reactor, passing sulfur-containing liquefied gas raw material (specific composition shown in Table 1) through a mass flow meter, and mixing with carrier gas (usually N) 2 ) Introducing into a fixed bed reactor together, and carrying out contact reaction at 40 ℃, wherein the volume space velocity of the reaction is 2000h -1 The sulfur content of the liquefied gas after the reaction was analyzed, and the results are shown in table 2.
TABLE 1
| Composition of | Content/% |
| C1～C2 | 5.8 |
| C3H8 | 38.6 |
| C3H6 | 36.5 |
| C4H10 | 19.0 |
| H 2 S | 50ppm |
| CH 3 SH | 50ppm |
TABLE 2
The data in the table show that the desulfurization adsorbent provided by the invention has far better effect than a commercial iron oxide desulfurizer when used for liquefied gas desulfurization, the sulfur content in the liquefied gas obtained by the method is lower than 1ppm, the liquefied gas obtained by the method is far better than that of the liquefied gas obtained by adopting a comparative example, and the desulfurization adsorbent has obvious effect.
According to the physicochemical property of the manganese oxide molecular sieve, the special crystal structure of the iron-based manganese oxide molecular sieve is fully utilized to fully exert the advantages of the iron-based manganese oxide molecular sieve in the field of liquefied gas desulfurization, so that the iron-based manganese oxide molecular sieve can have the sulfur capacity nearly six times that of commercial iron oxide at a lower temperature (60 ℃). Meanwhile, the desulfurization adsorbent has simple preparation method and good repeatability, and is 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 within the protective scope of the present invention.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it should be understood that various changes and modifications can be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A process for producing an ultra-low sulfur content liquefied gas comprising contacting a desulfurization adsorbent with a liquefied gas feedstock containing sulfur under conditions comprising: the temperature is normal temperature to 200 ℃, and the volume space velocity is 500 to 20000h -1 (ii) a The desulfurization adsorbent contains a carrier and an active component, wherein the carrier is a manganese oxide molecular sieve, and the active component is iron oxide.
2. The method of claim 1, wherein the manganese oxide molecular sieve is selected from one or more of birnessite, buchner, birnessite, bartonite, kalmanesite, and calciumlandite, and the iron oxide is selected from ferrous oxide (FeO), iron oxide (Fe £ oxide) 2 O 3 ) Ferroferric oxide (Fe) 3 O 4 ) One or more of (a).
3. The method according to claim 1, wherein the carrier is contained in an amount of 80 to 99.5 wt% as Fe based on the dry weight of the desulfurization adsorbent 2 O 3 The iron oxide content is 0.5-20 wt%.
4. The method of claim 1, wherein the contacting conditions comprise: the temperature is normal temperature to 150 ℃, and the volume space velocity is 800 to 10000h -1 。
5. The method as claimed in claim 1, wherein the sulfur-containing substances in the liquefied gas sulfur-containing raw material are one or more selected from hydrogen sulfide, mercaptan, disulfide, carbonyl sulfide and thioether, and the sulfur content in terms of sulfur element is 20-200ppm based on the total mass of the liquefied gas sulfur-containing raw material.
6. The method of claim 1, wherein the desulfurization adsorbent is prepared by a method a or a method b,
the method a comprises the following steps:
(a-1) dissolving a reduced manganese compound and an iron 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 and roasting the precipitate obtained in the step (a-2) to obtain the desulfurization adsorbent;
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 iron metal salt on the manganese oxide molecular sieve, and performing second drying and second roasting to obtain the desulfurization adsorbent.
7. The method of claim 6, wherein in method a and method b, the oxidized manganese compounds are respectively and independently selected from one or more of potassium permanganate, potassium permanganate and sodium permanganate, the iron metal salts are respectively and independently selected from one or more of ferric nitrate, ferric sulfide, ferric chloride, ferric citrate and ferric acetate, and the reduced manganese compounds 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 iron metal salt is (0.2 to 3): 1: (0.01-1).
8. The method according to claim 6, wherein in the step (a-3) of the method a, the drying temperature is 80-350 ℃ and the time is 1-24 h, the roasting temperature is 200-900 ℃ and the time is 0.5-12 h; 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.
9. The method according to claim 6, wherein between the step (a-2) and the step (a-2), a step of adding an acid to the mixed solution is further included, and the pH value of the mixed solution is adjusted to 0.2 to 3.
10. The method according to claim 6, wherein the hydrothermal reaction of the method b further comprises a step of adding an acid to the aqueous solution to adjust the pH of the aqueous solution to 0.2 to 3.
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| US20160175806A1 (en) * | 2014-12-17 | 2016-06-23 | University Of Connecticut | Adsorptive desulfurization |
| CN112691651A (en) * | 2020-12-22 | 2021-04-23 | 沈阳三聚凯特催化剂有限公司 | Preparation method of desulfurizer, desulfurizer and application |
| 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 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112691651A (en) * | 2020-12-22 | 2021-04-23 | 沈阳三聚凯特催化剂有限公司 | Preparation method of desulfurizer, desulfurizer and application |
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