This application is a 371 U.S. national phase of PCT/CN2021/090604, filed Apr. 28, 2021, which claims priority from ON patent application serial no, 202010391362.3, filed May 11, 2020, both which are incorporated by reference in its entirety.
The application belongs to the field of chemical technology, and specifically relates to a preparation method for producing acetaldehyde by catalyzing acetylene with ZAPO molecular sieve.
Acetaldehyde, also known as acetic aldehyde, belongs to aldehydes and is an organic compound with the molecular formula of CH3CHO or MeCHO. Acetaldehyde is regarded as one of the most important compounds among aldehydes due to its widespread presence in nature and large-scale industrial production, Acetaldehyde can be found in coffee, bread, and ripe fruits. It can also be produced as a metabolite via plants. Ethanol is oxidized into acetaldehyde, which is considered as the cause of hangover. Acetaldehyde is liquid at room temperature, colorless, flammable, and has a pungent odor. Its melting point is −123.5° and its boiling point is 20.2° C. Acetaldehyde can be reduced to ethanol or can be oxidized to acetic acid.
Acetaldehyde is an important basic organic chemical raw material that can be used for the production of acetic acid: acetic anhydride, ethyl acetate, butyraldehyde, butanol, pentaerythritol, pyridine and chloroacetaldehyde, etc. At present, there are mainly four methods for industrial production of acetaldehyde: (1) ethanol dehydrogenation or oxidation method; (2) light oil oxidation method; (3) ethylene direct oxidation method; (4) acetylene hydration method.
In recent years, due to the energy structure characterized by rich coal and less oil in China, the coal chemical industry has developed rapidly, and producing acetaldehyde by acetylene hydration has gradually become an advantageous process route. At present, the mainstream method for preparing acetaldehyde on the market also adopts the method of acetylene hydration production. In addition, in the traditional mercury-catalyzed acetylene hydration process for producing acetaldehyde, the mercury catalyst may cause serious harm to the human body and the environment, and the processing efficiency is relatively average.
In this regard, the present application proposes a new production process for preparing acetaldehyde by acetylene hydration and a catalyst system thereof, and the catalyst system does not contain mercury, so as to solve the problem that the conventional preparation methods of acetaldehyde on the market currently have ordinary efficiency and are more harmful to the environment.
In order to solve the above problems, the present application provides a preparation method for continuously producing acetaldehyde by catalyzing the gas phase hydration of acetylene with ZAPO molecular sieve. With reference to the drawings, the method specifically comprises the following steps:
The catalyst consumed due to abrasion must be replenished with fresh catalyst, which is periodically pressed from a catalyst replenishing hopper into the hydration reactor with nitrogen;
The catalyst in the hydration reactor continuously flows into a gas-solid nozzle via the pressure in the reactor, and is continuously transferred to a regenerator with nitrogen for regeneration; the compressed air from an outer tube enters the upper part of the regenerator through an air buffer for heat exchange before entering an air superheater, and then is transferred to the regenerator for regeneration after being heated, so as to burn off coke on the catalyst surface. The exhaust gas after regeneration firstly enters the internal cyclone separator to recover the catalyst particles, then passes through the external cyclone separator to capture the catalyst powder, and finally is vented by a tail gas water seal:
The regenerated catalyst naturally flows into the hydration reactor for further use.
The dilute acetaldehyde from the dilute acetaldehyde holding tank is pumped out by a dilute acetaldehyde feed pump, and then enters an acetaldehyde distillation column for distilling after being preheated by a preheater. The distilled water is returned to the water storage tank for reusing; the acetaldehyde vapor at the top of the column enters an acetaldehyde cooler and is condensed with −5° C. brine: the uncondensed gas is further condensed by the tail gas condenser; the condensate enters the gas-liquid separator for gas-liquid separation; the condensate enters the acetaldehyde intermediate trough, and then enters the acetaldehyde holding tank to obtain acetaldehyde product.
In step (1) of the present application, a molar ratio of water to acetylene n the feed gas ranges from 1 to 6.
In step (2) of the present application, the catalyst used in the hydration reaction is an active metal aluminophosphate molecular sieve type catalyst (ZAPO-5 molecular sieve catalyst) with Zn introduced into the molecular sieve framework structure.
In step (2) of the present application, the pressure in the fluidized bed hydration reactor is 0.5-1 kg/cm2, and the temperature is 290±10° C.
In step (2) of the present application, the temperature for the catalyst regeneration is 500-60° C.
The production process provided by the present application is simple and stable, can reasonably utilize the domestic energy structure in China, and the catalyst used is the currently more maturely studied ZAPO molecular sieve catalyst, which can not only notably reduce production costs and greatly increase production efficiency, but also completely solve the dependence on mercury catalysts in the production of acetaldehyde by acetylene hydration, such that the harm caused by mercury to the human body and the environment can be avoided. Also, by integrating the equipment with the method, the present application facilitates the production and utilization of the operator, and the use of raw materials is also recycled as many times as possible, which can effectively reduce the production cost and save resources at the same time.
The principles and features of the present application are described below, and the enumerated examples are only used for explaining the application, without limiting the scope of the present application.
As shown in
The catalyst consumed due to abrasion must be replenished with fresh catalyst, which is periodically pressed from catalyst replenishing hopper 110 into the hydration reactor 107 with nitrogen.
The catalyst in the hydration reactor 107 continuously flows into a gas-solid nozzle via the pressure in the reactor, and is continuously transferred to regenerator 111 with nitrogen for regeneration. The compressed air from an outer tube enters the upper part of the regenerator through air buffer 112 for heat exchange before entering an air superheater 113, and then is transferred to the regenerator 111 for regeneration after being heated, so as to burn off coke on the catalyst surface. The exhaust gas after regeneration firstly enters internal cyclone separator 114 to recover the catalyst particles, then passes through an external cyclone separator 115 to capture the catalyst powder, and finally is vented by tail gas water seal 116.
The regenerated catalyst naturally flows into the hydration reactor 107 for further use.
The dilute acetaldehyde from the dilute acetaldehyde holding tanks 121a and 121b is pumped out by dilute acetaldehyde feed pumps 128a and 128b, and then enters acetaldehyde distillation column 130 for distilling after being preheated by a preheater 129, The distilled water is returned to the water storage tank 100 for reusing. The acetaldehyde vapor at the top of the column enters acetaldehyde cooler 131 and is condensed with −5° C. brine. The uncondensed gas is further condensed by tail gas condenser 132. The condensate enters gas-liquid separators 133a and 133b for gas-liquid separation. The condensate enters acetaldehyde intermediate troughs 134a and 134b, and then enters acetaldehyde holding tank 135 to obtain acetaldehyde product.
In some embodiments, the present application relates to a preparation method for producing acetaldehyde by catalyzing acetylene with ZAPO molecular sieve, comprising:
In some embodiments, a molar ratio of the saturated steam to acetylene ranges from 1 to 6, e.g. from 2 to 4.5. As an example, a space velocity of acetylene can be 10-20 mL/min·mL catalyst, such as 13-16 mL/min·mL catalyst.
In some embodiments, the ZAPO catalyst is a ZAPO-5 molecular sieve catalyst. As an example, a molar ratio n(Zn):n(P2O5) of Zn content in the framework of the ZAPO-5 molecular sieve catalyst is 0.3-0.6, but is not limited thereto.
In some embodiments, the gas-solid phase catalytic reaction is performed under the following condition: a pressure of 0.5-1 kg/cm2 and a temperature of 290±10° C.
In some embodiments, the ZAPO catalyst is regenerated at a temperature of 500-600° C.
In some embodiments, the cooled brine is brine at −5° C.
In some embodiments, the cooled water is water at 5° C.
Herein, unless otherwise stated, each number or value representing reaction conditions, parameters, etc. is modified by the term “about” by default. In some embodiments, the term “about” should be understood a variation within ±1% relative to the object that it modifies.
Herein, unless otherwise stated, the terms “comprise”, “include” and “contain” or equivalents thereof are open-ended expression, and mean that elements, components and steps that are not specified may be included in addition to those listed.
Herein, unless otherwise stated, singular terms encompass plural referent and vice versa.
Herein, unless otherwise stated, the term “or” is intended to include “and” and vice versa.
All patents, patent applications and other established publications are expressly incorporated herein by reference for the purpose of describing and disclosing. These publications are provided solely because they were disclosed prior to the filing date of the present application. All statements regarding the dates of these documents or the representation of the contents of these documents are based on the information available to the applicant and do not constitute any admission as to the correctness of the dates of these documents or the contents of these documents. Moreover, in any country, any reference to these publications herein does not constitute an admission that the publications form part of the common knowledge in the art.
Unless otherwise stated, the reagents, materials, and devices used in the following Examples and Comparative Examples are all commercially available reagents, materials, and devices known in the art, Unless otherwise stated, the following operations are routine operations known in the art, which, for example, can be seen in the following description: Wang Zhikui et al., “Principle of Chemical Engineering (Fifth Edition)”, Chemical Industry Press, January 2018: Huang Xiaorong et at, “Introduction to Fine Chemical industry (Second Edition)”, Chemical Industry Press; March 2015; Zhang Chang et at, “Process Principle and Technology of Fine Chemical Industry”. Sichuan Science and Technology Press, October 2005.
With reference to the process flow shown in
The measured conversion rate of acetylene was 87.5%, and the selectivity of acetaldehyde was about 98%.
With reference to the process flow shown in
The measured conversion rate of acetylene was 94.2%, and the selectivity of acetaldehyde was about 99%.
With reference to the process flow shown in
The measured conversion rate of acetylene was 93.8%, and the selectivity of acetaldehyde was about 99%.
With reference to the process flow shown in
The measured conversion rate of acetylene was 93.5%, and the selectivity of acetaldehyde was about 99%.
The selectivities of acetaldehyde prepared by the process of Examples 1-4 are all 98% or more, and the conversion rates of raw material acetylene are 87.5% or more. It can be seen that the yield of acetaldehyde prepared by the method of the present application is extremely high, and the conversion rate of raw materials is also quite good, Compared with the traditional method, the method of the present application has higher yield and less pollution to the environment. Also, the catalyst has been recycled and reused for multiple times, and the undissolved acetaldehyde raw material has also been recycled and reused, which effectively save costs. The present application does not use the mercury catalyst in the traditional method, which effectively avoids the impact on operators/production environment, has high promotion value and commercial value, and is suitable for production use.
The above description shows and describes several preferred examples of the present invention. However, as mentioned above, it should be understood that the present application is not limited to the form disclosed herein, and should not be regarded as an exclusion of other embodiments, but can be used in various other combinations, modifications, and environments, and can be changed within the scope of the inventive concept described herein through the above teachings or the technology or knowledge in related art. Without departing from the spirit and scope of the present application, the modifications and changes made by those skilled in the art should fall within the protection scope of the appended claims of the present application.
Number | Date | Country | Kind |
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202010391362.3 | May 2020 | CN | national |
Filing Document | Filing Date | Country | Kind |
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PCT/CN2021/090604 | 4/28/2021 | WO |
Publishing Document | Publishing Date | Country | Kind |
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WO2021/227875 | 11/18/2021 | WO | A |
Number | Name | Date | Kind |
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3189556 | Dille | Jun 1965 | A |
3291839 | Carney et al. | Dec 1966 | A |
20050143597 | Mizushima | Jun 2005 | A1 |
Number | Date | Country |
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644834 | Aug 1984 | CH |
1592727 | Mar 2005 | CN |
102219660 | Oct 2011 | CN |
103113201 | May 2013 | CN |
108311174 | Jul 2018 | CN |
108993576 | Dec 2018 | CN |
111574344 | Aug 2020 | CN |
393690 | Jun 1933 | GB |
Entry |
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Number | Date | Country | |
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20230059377 A1 | Feb 2023 | US |