CN108970611B - Natural gas organic sulfur hydrolysis catalyst and preparation method thereof - Google Patents
Natural gas organic sulfur hydrolysis catalyst and preparation method thereof Download PDFInfo
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- CN108970611B CN108970611B CN201710399030.8A CN201710399030A CN108970611B CN 108970611 B CN108970611 B CN 108970611B CN 201710399030 A CN201710399030 A CN 201710399030A CN 108970611 B CN108970611 B CN 108970611B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 138
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 64
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 62
- 239000003345 natural gas Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000006229 carbon black Substances 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 6
- 150000000703 Cerium Chemical class 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 108
- 238000005096 rolling process Methods 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 38
- 239000011343 solid material Substances 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 21
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 239000008188 pellet Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 238000005507 spraying Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 6
- 239000000969 carrier Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012798 spherical particle Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 22
- 125000001741 organic sulfur group Chemical group 0.000 abstract description 22
- 238000000746 purification Methods 0.000 abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- 239000011593 sulfur Substances 0.000 abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000005303 weighing Methods 0.000 description 29
- 239000007789 gas Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 6
- 230000003301 hydrolyzing effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical group [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a natural gas organic sulfur hydrolysis catalyst and a preparation method thereof, which combines three components of alumina, titanium oxide and white carbon blackAs carrier, cerium and sodium are used as active components. The invention takes the three components of alumina, titanium oxide and white carbon black as a carrier and takes sodium salt and cerium salt as active components, and the specific surface of the prepared catalyst is more than 300m2The catalyst has the advantages of high activity stability, high organic sulfur hydrolysis rate of more than or equal to 99 percent, long service life of 6 years, simple preparation process and no secondary pollution in the preparation process, and the pore volume is more than 0.45 ml/g; under the condition that the environmental protection standard is increasingly improved, the catalyst is used for obviously improving the organic sulfur hydrolysis rate of the natural gas purification device, is beneficial to reducing the total sulfur content in the natural gas, and has obvious economic benefit and social benefit.
Description
Technical Field
The invention belongs to the technical field of sulfur recovery, and particularly relates to a natural gas organic sulfur hydrolysis catalyst and a preparation method thereof.
Background
Natural gas, as a high-quality, efficient and clean fossil energy, has been widely used in various fields of national life and production, and has reached about 25% of the primary energy consumption structure in the world, becoming an important energy source. In the early stage, the natural gas process development in China is slow. In recent years, China is actively developing the natural gas industry according to the requirements of sustainable development strategies and national policies on environmental protection. New high-sulfur large gas fields are developed, which place new demands on the natural gas purification process. Since 2012, the issuance and implementation of a new natural gas standard GB17820-2012 and the establishment of a new standard of atmospheric pollutant emission standard in the natural gas purification industry are to use CO in natural gas2The content and the total sulfur content are respectively 3 percent and 100mg/m3Reduced to 2% and 60mg/m3. Conventional naturalThe inadaptability of the gas purification technology is increasingly prominent. The upgrading of natural gas quality, the gradual decrease of tail gas emission and the increasingly complex gas composition become powerful power for promoting the progress of natural gas purification technology, and also provide new challenges for the natural gas purification technology.
The traditional natural gas purification process has strong selectivity for removing hydrogen sulfide, carbon dioxide or organic sulfur in raw material acid gas, but how to reduce the total sulfur content in product gas under the conditions of high flow rate and high pressure to ensure that the product gas meets the national pipe transportation requirement and meets the national environmental protection regulation requirement, the effective removal of the organic sulfur in the raw material gas must be considered.
A hydrolysis method for removing organic sulfur (particularly COS) contained in natural gas by hydrolysis using a low-temperature COS hydrolysis catalyst has become the most promising natural gas organic sulfur removal technology in recent years. The hydrolysis method has more advantages, such as low reaction temperature, low energy consumption, no hydrogen consumption, less side reactions and the like. The technology is combined with organic sulfur removal solvent to form the product which meets the organic sulfur quality standard of natural gas and Claus tail gas SO2One of the best solutions for emission standards. At present, in the biggest gas purification plant in China, the natural gas purification plant of the plain gas field of the central oil field division company in the petrochemical industry is provided with an organic sulfur hydrolysis unit at the front part of a sulfur recovery device so as to reduce the content of organic sulfur in natural gas. The core of the hydrolysis method for removing organic sulfur in natural gas is a hydrolysis catalyst. At present, the organic sulfur hydrolysis catalyst used by large-scale sulfur recovery devices at home and abroad has fewer types, the main component of the catalyst is generally aluminum oxide, and the catalyst has the characteristics of large specific surface area and good hydrolysis effect, but has the problems of poor hydrolysis activity and short service life of the catalyst. With the further improvement of environmental protection standards, it is a development direction of such catalysts to develop catalysts with good organic sulfur hydrolytic activity and stability, and to meet the requirements of sulfur recovery devices for large-scale natural gas fields.
Patent CN1069673 discloses a normal-temperature organic sulfur hydrolysis catalyst, which is spherical gamma-Al2O3Upper load 2-5% K2CO3The disadvantage of the catalyst is the treated raw gas COThe S content and the space velocity are both low and are respectively 1-5mg/m3And 2000h-1。
Patent CN00119385.6 describes a carbonyl sulfide hydrolysis catalyst, the composition of which is gamma-Al2O3：83％-97％，K2O: 2% -15%, BaO: 0.1 to 2 percent. The catalyst is prepared by an isometric solution impregnation method, and the catalyst is used for the catalyst with the COS content of less than 800mg/m at the temperature of 80-150 ℃ and the normal pressure3Space velocity of 6000-9000h-1And desulfurizing under the condition. The catalyst of the invention has high use temperature, generally above 80 ℃, and can not meet the low-temperature use requirement.
CN201010556207.9 introduces a catalyst for removing carbonyl sulfide in chemical production raw material gas, in particular to a catalyst containing magnesium-aluminum based hydrotalcite and gamma-Al2O3、TiO2The COS hydrolysis catalyst and the preparation method thereof. Is prepared from gamma-Al2O3，TiO2Mixing with Mg-Al-based hydrotalcite, kneading with water, extruding to form, drying and roasting to obtain carbonyl sulfide hydrolyzing catalyst product. The catalyst carrier disclosed by the patent is a titanium-aluminum composite carrier, the pore volume ratio of the catalyst is small, and the preparation cost is high.
U.S. Pat. No. 4,149,11668 discloses a method for preparing a catalyst from TiO2The catalyst for hydrolyzing COS, which is used as a carrier and at least contains one of alkali metal, alkaline earth metal, IIB group metal and IVA group metal as active components, has higher reaction temperature (200 ℃ C. and 400 ℃ C.), and uses titanium oxide as a carrier, so that the preparation cost is higher and the abrasion of the catalyst is large.
The catalyst takes alumina or titanium oxide as a carrier, and part of active components are added, and the defects are that: (1) the single-pure alumina is used as a carrier, the preparation cost of the catalyst is low, but the activity stability of the catalyst is poor, and the service life of the catalyst is shortened. (2) Titanium oxide is added as a carrier, so that the organic sulfur hydrolysis activity of the catalyst is improved, but the catalyst has higher abrasion and the pore volume ratio is reduced. (3) The hydrolysis reaction temperature of COS is high, and the airspeed of raw material gas is low.
Disclosure of Invention
The invention aims to provide a natural gas organic sulfur hydrolysis catalyst and a preparation method thereof, which solve the defects of the prior art.
The invention also provides a preparation method of the natural gas organic sulfur hydrolysis catalyst, which is scientific, reasonable, simple and feasible.
The invention relates to a natural gas organic sulfur hydrolysis catalyst, which takes three components of alumina, titanium oxide and white carbon black as a carrier and takes cerium and sodium as active components.
The raw materials comprise the following components in parts by weight:
wherein the active components are as follows:
4-8 parts of sodium oxide
2-6 parts of cerium oxide.
The natural gas organic sulfur hydrolysis catalyst adopts three components of alumina, titanium oxide and white carbon black to be combined and cooperated as a catalyst carrier, overcomes the defect of a single carrier, meets the requirements of the activity and the stability of the catalyst, ensures that the catalyst has a larger pore volume ratio, improves the effective reaction activity of the catalyst, and simultaneously reduces the preparation cost of the catalyst.
The alumina is used as a main carrier component, has the characteristics of large specific surface area and good hydrolysis effect, and has simple preparation process and low cost.
Titanium oxide has excellent alkaline catalytic action, and can effectively improve the hydrolytic activity of organic sulfur and promote the hydrolysis to be carried out as one of carrier components.
The white carbon black has higher pore volume, and can obviously improve the pore volume ratio of the catalyst and increase the effective area of catalytic reaction as one of carrier components, thereby increasing the low-temperature hydrolysis activity of the catalyst.
The catalyst sodium is added as an active component, so that the number of alkaline centers of the catalyst can be increased, the organic sulfur conversion activity is improved, and the low-temperature activity of the catalyst is improved. The addition of the rare earth metal cerium can modify the surface thermal stability of the alumina, so that the catalyst has good hydrothermal stability and promotes the organic sulfur hydrolysis reaction.
5-7 parts of sodium oxide and 3-5 parts of cerium oxide.
The precursor of the aluminum oxide is aluminum hydroxide quick-release powder, and the specific surface of the aluminum hydroxide quick-release powder is more than 250m2The pore volume is more than 0.20 ml/g; the precursor of the titanium oxide is metatitanic acid, and the specific surface area is more than 200m2The pore volume is more than 0.25 ml/g; the white carbon black is fumed silica, and the specific surface area is more than 250m2The pore volume is more than 0.55 ml/g.
The sodium oxide is added in the form of sodium carbonate; the cerium oxide is added in the form of cerium nitrate or cerium acetate.
In the preparation method of the natural gas organic sulfur hydrolysis catalyst, an auxiliary agent and a binder are added in the preparation process of the natural gas organic sulfur hydrolysis catalyst; based on 100 parts of the weight of the catalyst, the addition amount of the auxiliary agent is 1-5 parts, and the addition amount of the binder is 2-5 parts.
The addition amount of the auxiliary agent is preferably 2-4 parts, and the addition amount of the binder is preferably 2.5-3.5 parts. In the preparation process of the natural gas organic sulfur hydrolysis catalyst, an auxiliary agent needs to be added so as to further improve the specific surface area and the pore volume of the catalyst. In the preparation process of the natural gas organic sulfur hydrolysis catalyst, a binder is required to be added to enhance the strength of the catalyst.
The auxiliary agent is one of sesbania powder, polyvinyl alcohol, polyacrylamide and starch; the binder is one of acetic acid, nitric acid, citric acid, water glass or silica sol, and preferably citric acid.
The preparation method of the natural gas organic sulfur hydrolysis catalyst comprises the steps of uniformly mixing aluminum hydroxide quick-release powder, metatitanic acid, white carbon black, an auxiliary agent and a binder, rolling a ball, curing, drying and roasting to obtain a catalyst carrier, and soaking the carrier in an active component and then roasting to obtain a finished catalyst.
The preparation method of the natural gas organic sulfur hydrolysis catalyst comprises the following preparation steps:
(1) uniformly mixing aluminum hydroxide quick-release powder, metatitanic acid, white carbon black and an auxiliary agent to form a solid material;
(2) adding a binder into water, and uniformly stirring to prepare a solution A;
(3) rolling ball: putting the solid material into a ball rolling machine, spraying the solution A to the material in the ball rolling machine, rotating the ball to form the material until the material is formed into small balls with the diameter phi of 3-5mm, and screening the spherical particles to obtain the small balls with the diameter phi of 3-5 mm;
(4) curing, drying and roasting the pellets in a steam atmosphere to obtain a catalyst carrier;
(5) dipping: dissolving active components of sodium salt and cerium salt in water to prepare a solution B, and adding the carrier into the solution B to be soaked for 30min-3 h;
(6) drying: controlling the temperature of the impregnated carrier at 100 ℃ and 160 ℃, and drying for 2-6 hours;
(7) and (3) roasting the dried carrier for 3-8 hours at the temperature of 600 ℃ controlled at 360 ℃ to obtain the natural gas organic sulfur hydrolysis catalyst product.
In the step (5), the dipping time is preferably 1-2.5 h.
In the step (6), the drying temperature is preferably 120-140 ℃, and the drying time is preferably 3-5 h.
In the step (7), the roasting temperature is preferably 400-500 ℃, and the roasting time is preferably 4-6 h.
The method for preparing natural gas organosulfur hydrolysis catalyst according to claim 1, wherein in the step (4), the catalyst aging atmosphere is steam atmosphere, the aging temperature is 60-100 ℃, and the aging time is 10-30 h; the curing time is preferably 16-20h, and the curing temperature is preferably 80-100 ℃.
The drying temperature of the pellets is 70-150 ℃, and the drying time is 4-10 h; the drying temperature is preferably 100 ℃ to 130 ℃, and the drying time is preferably 6-9 h.
The roasting temperature of the pellets is 380-550 ℃, and the roasting time is 3-10 h. The roasting temperature is preferably 380-450 ℃, and the roasting time is preferably 4-6 h.
The specific surface of the aluminum hydroxide quick-release powder is preferably more than 300m2The pore volume is preferably 0.35 ml/g.
The natural gas organic sulfur hydrolysis catalyst is prepared by a rolling ball method.
The specific surface of the catalyst prepared by the invention is more than 300m2The catalyst has a pore volume of more than 0.45ml/g, a spherical particle shape, a specification of phi 3-5mm, an organic sulfur hydrolysis rate of more than or equal to 99 percent, and a service life of 6 years.
The natural gas organic sulfur hydrolysis catalyst is prepared by taking three components of alumina, titanium oxide and white carbon black as carriers and adding sodium salt and cerium salt as active components. The three carriers are combined for use, so that the defect of a single carrier is overcome, the requirements on the activity and the stability of the catalyst are met, the catalyst is ensured to have a large pore volume ratio, the effective reaction activity of the catalyst is improved, and the preparation cost of the catalyst is reduced. By adding sodium salt and rare earth element cerium as active components, the surface alkalinity of the catalyst is increased, and the low-temperature organic sulfur hydrolysis activity of the catalyst is greatly improved. The specific surface area and the pore volume of the catalyst are further improved by adding the auxiliary agent, and the catalyst is ensured to have higher hydrolytic activity. The catalyst is used for hydrolyzing organic sulfur in natural gas and reducing the total sulfur content in the natural gas.
Compared with the prior art, the invention has the following beneficial effects:
(1) the natural gas organic sulfur hydrolysis catalyst is prepared by using three components of alumina, titanium oxide and white carbon black as carriers and sodium salt and cerium salt as active components, wherein the specific surface area of the prepared catalyst is larger than 300m2The catalyst has a pore volume of more than 0.45ml/g, good activity stability, organic sulfur hydrolysis rate of more than or equal to 99 percent, and a service life of 6 years.
(2) The natural gas organic sulfur hydrolysis catalyst and the preparation method thereof have simple preparation process and no secondary pollution in the preparation process.
(3) Under the condition that the environmental protection standard is increasingly improved, the catalyst can obviously improve the organic sulfur hydrolysis rate of the natural gas purification device, is beneficial to reducing the total sulfur content in the natural gas, and has obvious economic benefit and social benefit.
Drawings
FIG. 1 is a flow chart of a catalyst activity evaluation apparatus.
Detailed Description
The present invention will be further described with reference to the following examples.
All catalyst activities in the examples were evaluated as follows:
the activity evaluation test of the catalyst is carried out on a 10mL micro-reverse activity evaluation device, a reactor is made of a stainless steel tube with the inner diameter of 20mm, the reactor is placed in a constant temperature box, and the specific process flow is shown in the figure. The loading amount of the catalyst is 10 mL/(20-40 meshes), and quartz sand with the same granularity is filled at the upper part for mixing and preheating. H in gas at the inlet and the outlet of the reactor is analyzed on line by adopting a Japanese Shimadzu GC-2014 gas chromatograph2S、COS、CO2The content of the sulfur compounds is determined by analyzing the constant quantity of the sulfur compounds by a TCD detector, GDX-301 is taken as a supporter, the column temperature is 120 ℃, hydrogen is taken as carrier gas, and the flow rate after column is 25 mL/min; the FPD detector analyzes trace sulfide, GDX-301 is used as a carrier, the column temperature is 80 ℃, nitrogen is used as a carrier gas, and the post-column flow rate is 30 mL/min.
With COS + H2O＝H2S+CO2For index reaction, the hydrolysis catalytic activity of the catalyst is considered, and the inlet gas volume composition is COS: 0.03% and CO2：3％、H2O: 3% and the balance of N2The gas volume space velocity is 5000h-1The reaction temperature was 60 ℃, and the hydrolysis rate of COS was calculated according to the following formula:
wherein: m0, M1 represent the volumetric concentration of COS at the inlet and outlet, respectively.
Example 1
Respectively weighing 1989g of aluminum hydroxide quick-release powder, 368g of metatitanic acid, 200g of white carbon black and 60g of polyvinyl alcohol, and uniformly mixing to form a solid material; weighing 60g of citric acid, adding the citric acid into water, and uniformly stirring to prepare a solution; putting the uniformly mixed solid material into a ball rolling machine, spraying citric acid solution on the material in the ball rolling machine, and rotating a rolling ball to form small balls with the diameter of phi 3-5 mm; curing the pellets in a water vapor atmosphere at 90 ℃ for 18h, drying at 120 ℃ for 6h, and roasting at 420 ℃ for 5h to obtain the catalyst carrier.
Weighing 205g of sodium carbonate and 202g of cerium nitrate, dissolving in water to prepare a solution, and adding the carrier into the solution for soaking for 2 hours; and drying the impregnated carrier at 130 ℃ for 4h, and roasting at 480 ℃ for 5h to obtain a finished catalyst A.
Example 2
Weighing 2295g of aluminum hydroxide quick-release powder, 245g of metatitanic acid, 100g of white carbon black and 60g of polyvinyl alcohol respectively, and uniformly mixing to form a solid material; weighing 60g of citric acid, adding the citric acid into water, and uniformly stirring to prepare a solution; putting the uniformly mixed solid material into a ball rolling machine, spraying citric acid solution on the material in the ball rolling machine, and rotating a rolling ball to form small balls with the diameter of phi 3-5 mm; curing the pellets in a water vapor atmosphere at 90 ℃ for 18h, drying at 120 ℃ for 6h, and roasting at 420 ℃ for 5h to obtain the catalyst carrier.
Weighing 274g of sodium carbonate and 101g of cerium nitrate, dissolving in water to prepare a solution, and adding the carrier into the solution for soaking for 2 hours; and drying the impregnated carrier at 130 ℃ for 4h, and roasting at 480 ℃ for 5h to obtain a finished catalyst B.
Example 3
1683g of aluminum hydroxide quick-release powder, 490g of metatitanic acid, 300g of white carbon black and 80g of polyvinyl alcohol are respectively weighed and evenly mixed to form a solid material; weighing 60g of citric acid, adding the citric acid into water, and uniformly stirring to prepare a solution; putting the uniformly mixed solid material into a ball rolling machine, spraying citric acid solution on the material in the ball rolling machine, and rotating a rolling ball to form small balls with the diameter of phi 3-5 mm; curing the pellets in a water vapor atmosphere at 90 ℃ for 18h, drying at 120 ℃ for 6h, and roasting at 420 ℃ for 5h to obtain the catalyst carrier.
Weighing 137g of sodium carbonate and 303g of cerium nitrate, dissolving in water to prepare a solution, and adding the carrier into the solution to be soaked for 2 hours; and drying the impregnated carrier at 130 ℃ for 4h, and roasting at 480 ℃ for 5h to obtain a finished catalyst product C.
Example 4
1836g of aluminum hydroxide quick-release powder, 490g of metatitanic acid, 200g of white carbon black and 80g of polyvinyl alcohol are respectively weighed and evenly mixed to form a solid material; weighing 80g of citric acid, adding the citric acid into water, and uniformly stirring to prepare a solution; putting the uniformly mixed solid material into a ball rolling machine, spraying citric acid solution on the material in the ball rolling machine, and rotating a rolling ball to form small balls with the diameter of phi 3-5 mm; curing the pellets in a water vapor atmosphere at 90 ℃ for 18h, drying at 120 ℃ for 6h, and roasting at 420 ℃ for 5h to obtain the catalyst carrier.
Weighing 171g of sodium carbonate and 252g of cerium nitrate, dissolving in water to prepare a solution, and adding the carrier into the solution for soaking for 2 hours; and drying the impregnated carrier at 130 ℃ for 4h, and roasting at 480 ℃ for 5h to obtain a catalyst finished product D.
Example 5
Respectively weighing 2142g of aluminum hydroxide quick-release powder, 294g of metatitanic acid, 160g of white carbon black and 40g of polyvinyl alcohol, and uniformly mixing to form a solid material; weighing 80g of citric acid, adding the citric acid into water, and uniformly stirring to prepare a solution; putting the uniformly mixed solid material into a ball rolling machine, spraying citric acid solution on the material in the ball rolling machine, and rotating a rolling ball to form small balls with the diameter of phi 3-5 mm; curing the pellets in a water vapor atmosphere at 90 ℃ for 18h, drying at 120 ℃ for 6h, and roasting at 420 ℃ for 5h to obtain the catalyst carrier.
239g of sodium carbonate and 151g of cerium nitrate are weighed and dissolved in water to prepare a solution, and the carrier is added into the solution to be soaked for 2 hours; and drying the impregnated carrier at 130 ℃ for 4h, and roasting at 480 ℃ for 5h to obtain a finished catalyst E.
Example 6
Respectively weighing 1989g of aluminum hydroxide quick-release powder, 441g of metatitanic acid, 140g of white carbon black and 50g of polyvinyl alcohol, and uniformly mixing to form a solid material; weighing 50g of citric acid, adding the citric acid into water, and uniformly stirring to prepare a solution; putting the uniformly mixed solid material into a ball rolling machine, spraying citric acid solution on the material in the ball rolling machine, and rotating a rolling ball to form small balls with the diameter of phi 3-5 mm; curing the pellets in a water vapor atmosphere at 90 ℃ for 18h, drying at 120 ℃ for 6h, and roasting at 420 ℃ for 5h to obtain the catalyst carrier.
Weighing 154g of sodium carbonate and 277g of cerium nitrate, dissolving in water to prepare a solution, and adding the carrier into the solution to be soaked for 2 hours; and drying the impregnated carrier at 130 ℃ for 4h, and roasting at 480 ℃ for 5h to obtain a finished catalyst F.
Example 7
Respectively weighing 1897g of aluminum hydroxide quick-release powder, 392g of metatitanic acid, 240g of white carbon black and 50g of polyvinyl alcohol, and uniformly mixing to form a solid material; weighing 50g of citric acid, adding the citric acid into water, and uniformly stirring to prepare a solution; putting the uniformly mixed solid material into a ball rolling machine, spraying citric acid solution on the material in the ball rolling machine, and rotating a rolling ball to form small balls with the diameter of phi 3-5 mm; curing the pellets in a water vapor atmosphere at 80 ℃ for 20h, drying at 100 ℃ for 9h, and roasting at 400 ℃ for 6h to obtain the catalyst carrier.
Weighing 188g of sodium carbonate and 227g of cerium nitrate, dissolving in water to prepare a solution, and adding the carrier into the solution for soaking for 1 hour; and drying the impregnated carrier at 120 ℃ for 5h, and roasting at 450 ℃ for 6h to obtain a finished catalyst G.
Example 8
Respectively weighing 2203g of aluminum hydroxide quick-release powder, 245g of metatitanic acid, 160g of white carbon black and 100g of polyvinyl alcohol, and uniformly mixing to form a solid material; weighing 100g of citric acid, adding the citric acid into water, and uniformly stirring to prepare a solution; putting the uniformly mixed solid material into a ball rolling machine, spraying citric acid solution on the material in the ball rolling machine, and rotating a rolling ball to form small balls with the diameter of phi 3-5 mm; curing the pellets in a water vapor atmosphere at 80 ℃ for 16h, drying at 130 ℃ for 6h, and roasting at 450 ℃ for 4h to obtain the catalyst carrier.
Weighing 222g of sodium carbonate and 177g of cerium nitrate, dissolving in water to prepare a solution, and adding the carrier into the solution to be soaked for 2.5 hours; and drying the impregnated carrier at 140 ℃ for 3H, and roasting at 500 ℃ for 6H to obtain a catalyst finished product H.
Example 9
Respectively weighing 2142g of aluminum hydroxide quick-release powder, 343g of metatitanic acid, 120g of white carbon black and 100g of polyvinyl alcohol, and uniformly mixing to form a solid material; weighing 100g of citric acid, adding the citric acid into water, and uniformly stirring to prepare a solution; putting the uniformly mixed solid material into a ball rolling machine, spraying citric acid solution on the material in the ball rolling machine, and rotating a rolling ball to form small balls with the diameter of phi 3-5 mm; curing the pellets in a water vapor atmosphere at 90 ℃ for 18h, drying at 120 ℃ for 6h, and roasting at 420 ℃ for 5h to obtain the catalyst carrier.
Weighing 257g of sodium carbonate and 126g of cerium nitrate, dissolving in water to prepare a solution, and adding the carrier into the solution for soaking for 2 hours; and drying the impregnated carrier at 130 ℃ for 4h, and roasting at 480 ℃ for 5h to obtain a finished catalyst I.
Comparative example 1
Respectively weighing 2754g of aluminum hydroxide quick-release powder and 60g of polyvinyl alcohol, and uniformly mixing to form a solid material; weighing 60g of citric acid, adding the citric acid into water, and uniformly stirring to prepare a solution; putting the uniformly mixed solid material into a ball rolling machine, spraying citric acid solution on the material in the ball rolling machine, and rotating a rolling ball to form small balls with the diameter of phi 3-5 mm; curing the pellets in a water vapor atmosphere at 90 ℃ for 18h, drying at 120 ℃ for 6h, and roasting at 420 ℃ for 5h to obtain the catalyst carrier.
Weighing 205g of sodium carbonate and 202g of cerium nitrate, dissolving in water to prepare a solution, and adding the carrier into the solution for soaking for 2 hours; and drying the impregnated carrier at 130 ℃ for 4h, and roasting at 480 ℃ for 5h to obtain a finished catalyst J.
Comparative example 2
Weighing 2295g of aluminum hydroxide quick-release powder, 368g of metatitanic acid, 200g of white carbon black and 60g of polyvinyl alcohol respectively, and uniformly mixing to form a solid material; weighing 60g of citric acid, adding the citric acid into water, and uniformly stirring to prepare a solution; putting the uniformly mixed solid material into a ball rolling machine, spraying citric acid solution on the material in the ball rolling machine, and rotating a rolling ball to form small balls with the diameter of phi 3-5 mm; curing the pellets in a steam atmosphere at 90 ℃ for 18h, drying at 120 ℃ for 6h, and roasting at 420 ℃ for 5h to obtain a catalyst finished product K.
Table 1 shows the main preparation conditions of the above examples and comparative examples.
TABLE 1 preparation parameters for examples 1-9 and comparative examples 1-2
The physical properties of the catalysts obtained in examples 1 to 9 and comparative examples 1 to 2 were measured and the activity was evaluated according to the above-mentioned methods, and the data are shown in Table 2.
TABLE 2 comparison of physico-chemical Properties of catalysts obtained in examples 1-9 and comparative examples 1-2
As can be seen from the data in Table 2, the catalyst activity evaluations in the examples and comparative examples were performed at 60 deg.C, while the catalysts of examples 1-9 had significantly higher activity than the catalysts of comparative examples 1,2, indicating that the catalysts of the present invention have a higher pore volume ratio and good low temperature catalytic activity.
Claims (13)
1. A natural gas organic sulfur hydrolysis catalyst is characterized in that: the preparation method comprises the following steps of (1) taking three components of alumina, titanium oxide and white carbon black as carriers, and taking cerium and sodium as active components;
the raw materials comprise the following components in parts by weight:
55-75 parts of alumina
10-20 parts of titanium oxide
5-15 parts of white carbon black
Active component 10 parts
Wherein the active components are as follows:
4-8 parts of sodium oxide
2-6 parts of cerium oxide;
the preparation method of the natural gas organic sulfur hydrolysis catalyst comprises the following steps: an auxiliary agent and a binder are added in the preparation process of the natural gas organic sulfur hydrolysis catalyst; based on 100 parts of the weight of the catalyst, the addition amount of the auxiliary agent is 1-5 parts, and the addition amount of the binder is 2-5 parts.
2. The natural gas organosulfur hydrolysis catalyst according to claim 1, characterized in that: 5-7 parts of sodium oxide and 3-5 parts of cerium oxide.
3. The natural gas organosulfur hydrolysis catalyst of claim 1, wherein the precursor of the aluminum oxide is aluminum hydroxide fast-release powder having a specific surface area greater than 250m2The pore volume is more than 0.20 ml/g.
4. The natural gas organosulfur hydrolysis catalyst according to claim 1, characterized in that: the precursor of the titanium oxide is metatitanic acid, and the specific surface area is more than 200m2The pore volume is more than 0.25 ml/g.
5. The natural gas organosulfur hydrolysis catalyst according to claim 1, characterized in that: the white carbon black is fumed silica, and the specific surface area is more than 250m2The pore volume is more than 0.55 ml/g.
6. The natural gas organosulfur hydrolysis catalyst according to claim 1, characterized in that: the sodium oxide is added in the form of sodium carbonate; the cerium oxide is added in the form of cerium nitrate or cerium acetate.
7. The natural gas organosulfur hydrolysis catalyst according to claim 1, characterized in that: the auxiliary agent is one of sesbania powder, polyvinyl alcohol, polyacrylamide or starch.
8. The natural gas organosulfur hydrolysis catalyst according to claim 1, characterized in that: the binder is one of acetic acid, nitric acid, citric acid, water glass or silica sol.
9. The natural gas organosulfur hydrolysis catalyst according to claim 1, characterized in that: the preparation method of the natural gas organic sulfur hydrolysis catalyst comprises the steps of uniformly mixing aluminum hydroxide quick-release powder, metatitanic acid, white carbon black, an auxiliary agent and a binder, rolling a ball, curing, drying and roasting to prepare a catalyst carrier, and roasting the carrier after dipping an active component to prepare a finished catalyst.
10. The natural gas organosulfur hydrolysis catalyst according to claim 1, characterized in that: the preparation method comprises the following preparation steps:
(1) uniformly mixing aluminum hydroxide quick-release powder, metatitanic acid, white carbon black and an auxiliary agent to form a solid material;
(2) adding a binder into water, and uniformly stirring to prepare a solution A;
(3) rolling ball: putting the solid material into a ball rolling machine, spraying the solution A to the material in the ball rolling machine, rotating the ball to form the material until the material is formed into small balls with the diameter phi of 3-5mm, and screening the spherical particles to obtain the small balls with the diameter phi of 3-5 mm;
(4) curing, drying and roasting the pellets in a steam atmosphere to obtain a catalyst carrier;
(5) dipping: dissolving active components of sodium salt and cerium salt in water to prepare a solution B, and adding the carrier into the solution B to be soaked for 30min-3 h;
(6) drying: controlling the temperature of the impregnated carrier at 100 ℃ and 160 ℃, and drying for 2-6 hours;
(7) and (3) roasting the dried carrier for 3-8 hours at the temperature of 600 ℃ controlled at 360 ℃ to obtain the natural gas organic sulfur hydrolysis catalyst product.
11. The natural gas organosulfur hydrolysis catalyst of claim 10, characterized in that: in the step (4), the curing atmosphere of the catalyst is a water vapor atmosphere, the curing temperature is 60-100 ℃, and the curing time is 10-30 h.
12. The method of preparing a natural gas organosulfur hydrolysis catalyst according to claim 10, characterized in that: in the step (4), the drying temperature of the pellets is 70-150 ℃, and the drying time is 4-10 h.
13. The natural gas organosulfur hydrolysis catalyst of claim 10, characterized in that: in the step (4), the roasting temperature of the pellets is 380-550 ℃, and the roasting time is 3-10 h.
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