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Copper-chromium catalyst, preparation method thereof and method for preparing alkanol by olefine aldehyde or aldehyde hydrogenation

A catalyst, copper chromium technology, applied in the field of catalysis, can solve the problems of hidden safety hazards of production personnel, long process, large loss of metal salt raw materials, etc., and achieve the elimination of waste liquid containing metal ions, simple production process and high hydrogenation activity Effect

Pending Publication Date: 2021-06-18
CHINA NAT OFFSHORE OIL CORP +4
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The existing process of preparing copper-chromium catalysts by co-precipitation method not only has a long process, but also has a large loss of metal salt raw materials due to the difference in the pH value of the precipitate formed by different types of metal salts.
In particular, chromium ions in waste liquid are easily absorbed by nitrate ions (NO 3 ﹣ ) oxidation to form high-valent chromium ions (such as Cr 6+ ), there are hidden dangers to the environment and the personal safety of production personnel

Method used

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  • Copper-chromium catalyst, preparation method thereof and method for preparing alkanol by olefine aldehyde or aldehyde hydrogenation
  • Copper-chromium catalyst, preparation method thereof and method for preparing alkanol by olefine aldehyde or aldehyde hydrogenation
  • Copper-chromium catalyst, preparation method thereof and method for preparing alkanol by olefine aldehyde or aldehyde hydrogenation

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preparation example Construction

[0058] The inventors have provided an efficient and clean copper-chromium catalyst and a preparation method thereof through in-depth research on the nature of the active center of the copper-chromium catalyst and the reaction type in the catalyst preparation process. refer to figure 1 , the preparation method of a kind of copper chromium catalyst provided by one embodiment of the present invention comprises:

[0059] S10: providing an aqueous solution comprising copper salt and chromium salt;

[0060] S20: providing a reducing aqueous solution;

[0061] S30: forming a gel;

[0062] S40: drying;

[0063] S50: Roasting.

[0064] In the step S10 of providing the reaction solution, it includes: providing an aqueous solution comprising copper salt and chromium salt, wherein at least one of the copper salt and the chromium salt should use nitrate as an anion, for example, an aqueous solution of copper nitrate and chromium nitrate can be used as The reaction solution. The react...

Embodiment 1

[0107] Measure 263.98mL of copper nitrate solution (concentration is 1.0mol / L) and 184.22mL of chromium nitrate solution (concentration is 1.0mol / L) respectively, and place them in a glass reactor with a stirring and heating jacket with a volume of 600mL. The ratio of copper to chromium is 1.43:1; start stirring and feed heat transfer oil, control the temperature in the reactor to 90°C; simultaneously add a total of 1186mL oxalic acid solution (concentration of 1.0mol / L) dropwise to the reactor , the molar ratio of oxalic acid to total nitrates was 1.1:1); the condensed collected evaporated water reached 1300mL and then stopped stirring to obtain 175g of gel. Gained gel is placed in the enamel dish, and is dried at 120 DEG C for 12 hours; The solid after drying is calcined at 300 DEG C for 4 hours, obtains the total 34.8g of black powder A, and the yield of metal ions is 99.42% (the yield of metal ions is according to Calculated by the following formula: mass of black powder A...

Embodiment 2

[0110] Measure 241.98mL of copper nitrate solution (concentration: 1.0mol / L) and 207.25mL of chromium nitrate solution (concentration: 1.0mol / L), and place them in a jacketed glass reactor with a volume of 600mL, in which copper and chromium The mass ratio is 1.17:1; start stirring and feed heat transfer oil, control the temperature in the reactor to 80°C; simultaneously add a total of 1106mL oxalic acid solution (concentration is 1.0mol / L, oxalic acid and total nitric acid The molar ratio of root is 1.0:1); Condensation collects evaporated water and stops stirring after reaching 1230mL, obtains 174g gel. The obtained gel was placed in an enamel dish and dried at 120° C. for 12 hours, and the dried solid was fired at 350° C. for 4 hours to obtain 34.9 g of black powder B (99.6% yield of metal ions). The black powder B was compressed into tablets by a tableting method, and the tableting pressure was 7.0 MPa to obtain catalyst B.

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Abstract

The invention discloses a copper-chromium catalyst, a preparation method thereof and a method for preparing alkanol by olefine aldehyde or aldehyde hydrogenation. The method comprises the following steps of providing an aqueous solution containing a copper salt and a chromium salt as a reaction solution, and heating for gelation to obtain a precursor, wherein anions in the copper salt and / or the chromium salt contain nitrate radicals, the reaction liquid contains an additive, and the additive is a reducing substance and / or a raw material which can be decomposed to generate the reducing substance in the heating gelation process, and drying and roasting the precursor to obtain the copper-chromium catalyst. According to the method, the problem that chromium ions are oxidized by NO3<-> is effectively relieved, and Cu in the obtained catalyst can exist in the form of CuO. Therefore, the thermal stability of the catalyst in the hydrogenation activation process is improved, and the phenomenon of sharp temperature rise is avoided. In addition, the hydrogenation activity and selectivity of the catalyst can be further improved through the method provided by the invention.

Description

technical field [0001] The invention belongs to the technical field of catalysis, and in particular relates to a copper chromium catalyst, a preparation method thereof and a method for preparing alkanol by hydrogenating alkenal or aldehyde. Background technique [0002] The formation of aldehydes with one more carbon atom from olefins with carbon monoxide and hydrogen under the action of a catalyst is a well-known process. Aldehydes can be directly hydrogenated to give alcohols, or can be condensed to give alkenals and then hydrogenated to finally give alcohols. One of the main uses of these alcohols is as a plasticizer after esterification with collar phthalate, used in PVC, such as the traditional plasticizer 2-ethylhexanol (dioctyl phthalate, or DOP) , butanol (dibutyl phthalate, or DBP). A large number of animal experiments have confirmed the potential carcinogenicity of DOP and DBP. Therefore, in recent years, developed countries such as Europe, America and Japan have...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/86B01J35/10B01J37/03C07C29/141C07C31/12C07C29/17C07C31/125
CPCB01J23/868B01J37/036C07C29/175C07C29/141B01J35/613B01J35/633B01J35/647C07C31/125C07C31/12
Inventor 傅送保姚志龙侯章贵王淇峰陈和赵雨薛洪健孙培永张卉张胜红
Owner CHINA NAT OFFSHORE OIL CORP
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