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CN-119158623-B - Preparation method of immobilized low-carbon hydrocarbon alkali-free deodorization catalyst

CN119158623BCN 119158623 BCN119158623 BCN 119158623BCN-119158623-B

Abstract

The invention discloses a preparation method of an immobilized low-carbon hydrocarbon deodorization catalyst. The preparation method comprises the steps of (1) preparing a solution containing M 2+ and M' 3+ , adding a molecular sieve, stirring uniformly, (2) reacting the obtained suspension with a mixed solution of NaOH and Na 2 CO 3 or weak base solution under stirring, (3) drying and roasting to obtain a composite carrier, (4) preparing a cobalt-containing salt solution, exchanging Co 2+ on the composite carrier in an ion exchange mode, (5) filtering and drying to obtain solid alkali of the Co molecular sieve, (6) adding the solid alkali of the Co molecular sieve, ammonium phthalate sulfonate, urea, ammonium molybdate and phthalic anhydride according to a proportion, grinding uniformly, and (7) heating the obtained material under an inert atmosphere for reaction to obtain the catalyst product. The sulfonated cobalt phthalocyanine in the catalyst prepared by the invention is combined with the molecular sieve through chemical bonds, so that the combination firmness of active components is higher, and the catalyst has longer service life.

Inventors

  • MENG FANZHONG
  • WANG LUYAO
  • LI YONG
  • FAN DEQUAN

Assignees

  • 中国石油化工股份有限公司
  • 中石化（大连）石油化工研究院有限公司

Dates

Publication Date
20260505
Application Date
20230619

Claims (11)

  1. 1. The preparation method of the immobilized low-carbon hydrocarbon alkali-free deodorization catalyst comprises the following steps: (1) Preparing a mixed solution containing M 2+ and M' 3+ with a certain concentration, adding the micro-mesoporous molecular sieve into the mixed solution, and uniformly stirring; (2) Reacting the suspension obtained in the step (1) with NaOH, na 2 CO 3 mixed solution or weak base solution for a period of time under stirring; (3) Filtering, washing, drying and roasting the material obtained in the step (2) to obtain a composite carrier; (4) Preparing a cobalt-containing salt solution, and exchanging Co 2+ onto the composite carrier obtained in the step (3) in an ion exchange mode; (5) Filtering and drying the material obtained in the step (4) to obtain Co molecular sieve solid alkali; (6) Adding a certain amount of ammonium phthalate sulfonate, urea, ammonium molybdate and phthalic anhydride into the Co molecular sieve obtained in the step (5) according to a certain proportion, and uniformly grinding; (7) Placing the material obtained in the step (6) in a reactor, heating to 80-160 ℃ under inert atmosphere, stabilizing for 3-8 h, and heating to 180-300 ℃ for reacting for 3-8 h to obtain a catalyst product; wherein M is an element of IIA or IIB, M' is an element of IIIA or VIII, and the molar ratio of silicon to aluminum of the molecular sieve is 0.5-200.
  2. 2. The method according to claim 1, wherein the stirring time in the step (1) is 10min to 180min.
  3. 3. The method of claim 1, wherein M is at least one of the divalent metals selected from Mg, ca, ba, zn and M' is at least one of the trivalent metals selected from Al, fe, co, ni.
  4. 4. The preparation method of claim 1, wherein the mixed solution containing M 2+ and M ' 3+ is a nitrate solution or a hydrochloride solution of M and M', the concentration of the mixed solution containing M 2+ and M ' 3+ is 0.1 mol/L-saturated concentration and 0.02 mol/L-saturated concentration, and the molar ratio of M 2+ to M' 3+ is 0.5-30.
  5. 5. The preparation method of the aqueous ammonia solution according to claim 1, wherein the molar ratio of NaOH to Na 2 CO 3 in the mixed solution in the step (2) is 1:3-30:1, and the weak base solution is at least one selected from dilute ammonia water and dimethyl ammonia.
  6. 6. The method according to claim 1, wherein stirring is stopped when the pH of the suspension in the step (2) is 9 to 10, and the suspension is allowed to stand for 10 to 180 minutes.
  7. 7. The preparation method of the ceramic material according to claim 1, wherein the roasting condition in the step (3) is that the temperature is 400-900 ℃ and the roasting time is 4-10h.
  8. 8. The method of claim 1, wherein the cobalt-containing salt solution of step (4) is selected from at least one of a Co (NO 3 ) 2 solution, A Co (AC) 2 solution, or a CoCl 2 solution.
  9. 9. The preparation method of claim 1, wherein the ion exchange in the step (4) is performed under the conditions that the temperature is normal temperature to 200 ℃ and the exchange time is 12 to 36 hours.
  10. 10. An immobilized low-carbon hydrocarbon alkali-free deodorization catalyst obtained by the preparation method of any one of claims 1 to 9.
  11. 11. The alkali-free deodorizing catalyst according to claim 10, wherein the catalyst comprises, in weight content, 35% -65% of molecular sieve, 35% -55% of xMO @ yM @ 2 O 3 % -55% of sulfonated cobalt phthalocyanine, 5% -25% of sulfonated cobalt phthalocyanine, wherein M is at least one of divalent metals selected from Mg, ca, ba, zn, M' is at least one of trivalent metals selected from Al, fe, co, ni, and x: y = 0.5-30.

Description

Preparation method of immobilized low-carbon hydrocarbon alkali-free deodorization catalyst Technical Field The invention belongs to the field of petrochemical industry, relates to a preparation method of a catalyst suitable for alkali-free deodorization of low-carbon hydrocarbons, and in particular relates to a preparation method of an immobilized catalyst applied to an alkali-free deodorization process of C3-C8 hydrocarbons. Background The most widely applied technology in the low-carbon hydrocarbon deodorization process is a merokes extraction oxidation process, the basic principle is that sodium mercaptide is generated by absorbing mercaptan by alkali liquor, then sodium mercaptide is oxidized into disulfide and alkali by air under the action of a water-soluble cobalt phthalocyanine catalyst, and the disulfide removal and alkali liquor regeneration are realized by separating the disulfide from the alkali liquor. The technology mainly has the problems of large alkaline residue emission, high alkaline residue treatment difficulty, environmental protection, easy coalescence and inactivation of water-soluble cobalt phthalocyanine and high operation cost. In order to solve the problem, UOP provides a fixed bed mercaptan removal process, and the core is that a cobalt phthalocyanine active component and solid alkali are dispersed and loaded on a porous carrier to realize the purpose of removing mercaptan by one-step catalytic oxidation. U.S. patent No. 2988500 discloses a supported cobalt phthalocyanine catalyst, wherein cobalt phthalocyanine is supported on activated carbon, and thiol is catalytically oxidized under the action of a soluble alkali reagent. Chinese patent CN1200958a discloses a catalyst with a complex supported on the surface of a solid basic oxide, where the complex is formed by sulfonate cobalt phthalocyanine or carboxylate cobalt phthalocyanine having a negative ion group and quaternary ammonium salt cobalt phthalocyanine having a positive ion group, and the oxidation reaction of the catalyst does not need to add an alkali solution, so that the activity and stability are improved to a certain extent. The preparation method of the catalyst adopts a loading mode, and the catalyst is dried at normal temperature or lower temperature after loading, so that the loading stability of the active component is poor, and the active component is partially shed under higher airspeed or along with the prolongation of reaction time, so that the catalytic activity is reduced, even deactivated. Disclosure of Invention Based on the problems existing in the prior art, the invention provides a preparation method of an immobilized low-carbon hydrocarbon alkali-free deodorization catalyst. The catalyst can remove mercaptan substances in low-carbon hydrocarbon under the alkali-free condition, and the active components are combined with the carrier in a bonding mode, so that the situation of falling off and inactivation is not easy to occur in the reaction process, the stability of the catalyst is greatly improved, and the operation cost is reduced. The invention provides a preparation method of an immobilized low-carbon hydrocarbon alkali-free deodorization catalyst, which comprises the following steps: (1) Preparing a mixed solution containing M 2+ and M' 3+ with a certain concentration, adding the micro-mesoporous molecular sieve into the mixed solution, and uniformly stirring; (2) Reacting the suspension obtained in the step (1) with NaOH, na 2CO3 mixed solution or weak base solution for a period of time under stirring; (3) Filtering, washing, drying and roasting the material obtained in the step (2) to obtain a composite carrier; (4) Preparing a cobalt-containing salt solution, and exchanging Co 2+ onto the composite carrier obtained in the step (3) in an ion exchange mode; (5) Filtering and drying the material obtained in the step (4) to obtain Co molecular sieve and solid alkali; (6) Adding a certain amount of ammonium phthalate sulfonate, urea, ammonium molybdate and phthalic anhydride into the Co molecular sieve and solid alkali obtained in the step (5) according to a certain proportion, and uniformly grinding; (7) And (3) placing the material obtained in the step (6) in a reactor, heating to 80-160 ℃ under inert atmosphere, stabilizing for 3-8 h, and heating to 180-300 ℃ for reacting for 3-8 h to obtain the catalyst product. Further, the stirring time in the step (1) is generally 10min to 180min, preferably 60min to 120min. Further, in the mixed solution of the step (1), M is a group IIA or group IIB element, M 'is a group IIIA or group VIII element, preferably M is at least one of divalent metals selected from Mg, ca, ba, zn, and M' is at least one of trivalent metals selected from Al, fe, co, ni. The mixed solution containing M 2+ and M '3+ may be a nitrate solution or a hydrochloride solution of M and M'. The concentration of the mixed solution containing M 2+ and M' 3+ is generally 0.1 mol/L-saturated