阅读说明：本技术 不饱和烃气的脱氧方法 (Method for deoxidizing unsaturated hydrocarbon gas ) 是由 文松 赵磊 姜杰 徐伟 于 2020-04-10 设计创作，主要内容包括：本发明涉及脱氧技术领域,公开了一种不饱和烃气的脱氧方法,包括：步骤S10、待脱氧的不饱和烃气中的部分不饱和烃气在起始催化剂的作用下进行反应得到脱氧后的不饱和烃气；步骤S20、将待脱氧的不饱和烃气中的剩余的不饱和烃气分为多个部分,使得每部分待脱氧的不饱和烃气和前一步骤所获得的脱氧后的不饱和烃气在相应的催化剂的作用下共同进行反应,得到脱氧后的不饱和烃气。该不饱和烃气的脱氧方法使得待除氧的不饱和烃气进行逐步反应,提高了除氧效果。(The invention relates to the technical field of deoxidation, and discloses a deoxidation method of unsaturated hydrocarbon gas, which comprises the following steps: step S10, reacting part of unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxidized under the action of an initial catalyst to obtain deoxidized unsaturated hydrocarbon gas; step S20, dividing the remaining unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxygenated into a plurality of parts, so that each part of the unsaturated hydrocarbon gas to be deoxygenated and the deoxygenated unsaturated hydrocarbon gas obtained in the previous step react together under the action of a corresponding catalyst to obtain the deoxygenated unsaturated hydrocarbon gas. The unsaturated hydrocarbon gas deoxidation method enables the unsaturated hydrocarbon gas to be deoxidized to gradually react, and improves the deoxidization effect.)

1. A method for deoxidizing an unsaturated hydrocarbon gas, comprising:

step S10, reacting part of unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxidized under the action of an initial catalyst to obtain deoxidized unsaturated hydrocarbon gas;

step S20, dividing the remaining unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxygenated into a plurality of parts, so that each part of the unsaturated hydrocarbon gas to be deoxygenated and the deoxygenated unsaturated hydrocarbon gas obtained in the previous step react together under the action of a corresponding catalyst to obtain the deoxygenated unsaturated hydrocarbon gas.

2. The method for deoxidizing unsaturated hydrocarbon gas as claimed in claim 1, wherein, in the step S10, the reaction amount of the partially unsaturated hydrocarbon gas is 2% to 40% of the total amount of the unsaturated hydrocarbon gas to be deoxidized.

3. The method for deoxidizing unsaturated hydrocarbon gas as set forth in claim 2, wherein the reaction amount of said partially unsaturated hydrocarbon gas is 5% to 30% of the total amount of said unsaturated hydrocarbon gas to be deoxidized.

4. The method for deoxidizing unsaturated hydrocarbon gas as claimed in claim 1, wherein in the step S20, the remaining unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxidized is divided into 2 to 20 portions, and preferably, the remaining unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxidized is divided into 3 to 10 portions.

5. The unsaturated hydrocarbon gas deoxidation method according to claim 4, characterized in that in the step S20, the reaction temperature can be controlled at 50-580 ℃ for each part of the reaction, preferably at 60-450 ℃; and/or

In the step S20, the reaction space velocity is controlled at 500 per part of reaction^-1-45000h^-1(ii) a Preferably, the reaction space velocity is controlled at 1000^-1-22000h^-1。

6. The method for deoxidizing unsaturated hydrocarbon gas, according to claim 4, wherein the remaining unsaturated hydrocarbon gas is divided into a first part of unsaturated hydrocarbon gas, a second part of unsaturated hydrocarbon gas, and a third part of unsaturated hydrocarbon gas; the step S20 includes:

step S20a, reacting the first part of unsaturated hydrocarbon gas and the deoxidized unsaturated hydrocarbon gas obtained in step S10 together under the action of a first catalyst to obtain a first deoxidized unsaturated hydrocarbon gas;

step S20b, reacting the second part of unsaturated hydrocarbon gas and the first deoxidized unsaturated hydrocarbon gas obtained in step S20a together under the action of a second catalyst to obtain a second deoxidized unsaturated hydrocarbon gas;

step S20c, reacting the third part of unsaturated hydrocarbon gas and the second deoxidized unsaturated hydrocarbon gas obtained in step S20b together under the action of a third catalyst to obtain a third deoxidized unsaturated hydrocarbon gas.

7. The method for deoxidizing unsaturated hydrocarbon gas as set forth in claim 6,

in the step S20a, the reaction amount of the first part of unsaturated hydrocarbon gas is 10% to 30% of the total amount of the unsaturated hydrocarbon gas to be deoxygenated;

in the step S20b, the reaction amount of the second part of unsaturated hydrocarbon gas is 15 to 40% of the total amount of the unsaturated hydrocarbon gas to be deoxygenated;

in the step S20c, the reaction amount of the third part of the unsaturated hydrocarbon gas is 15% to 30% of the total amount of the unsaturated hydrocarbon gas to be deoxygenated.

8. The unsaturated hydrocarbon gas deoxidation method according to claim 6, characterized in that in the step S20a, the reaction temperature can be controlled at 40-200 ℃; preferably, the reaction temperature can be controlled between 60 ℃ and 185 ℃.

9. The method for deoxidizing unsaturated hydrocarbon gas as claimed in claim 6, wherein in said step S20a, the reaction space velocity is controlled to 500^-1-45000h^-1(ii) a Preferably, the reaction space velocity is controlled at 1000^-1-22000h^-1。

10. The unsaturated hydrocarbon gas deoxidation method claimed in claim 6, wherein in said step S20b, the reaction temperature can be controlled at 380 ℃ of 100, preferably at 145 ℃ to 325 ℃.

11. The method for deoxidizing unsaturated hydrocarbon gas as claimed in claim 6, wherein in said step S20b, the reaction space velocity is controlled to 500^-1-45000h^-1(ii) a Preferably, the reaction space velocity is controlled at 1200^-1-22000h^-1。

12. The unsaturated hydrocarbon gas deoxidation method according to claim 6, characterized in that, in the step S20c, the reaction temperature can be controlled at 175 ℃ to 580 ℃; preferably, the reaction temperature can be controlled between 225 ℃ and 450 ℃.

13. The method for deoxidizing unsaturated hydrocarbon gas as claimed in claim 6, wherein in said step S20c, the reaction space velocity is controlled to be 500h^-1-45000h^-1(ii) a Preferably, the reaction space velocity is controlled at 1500^-1-22000h^-1。

14. The unsaturated hydrocarbon gas deoxidation method according to claim 1, characterized in that in the step S10, the reaction temperature can be controlled at 30 ℃ to 200 ℃; preferably, the reaction temperature can be controlled between 40 ℃ and 180 ℃.

15. The unsaturated hydrocarbon gas deoxidation method according to claim 1, characterized in that in the step S10, the partially unsaturated hydrocarbon gas is heated to 30 ℃ to 160 ℃, preferably, the partially unsaturated hydrocarbon gas is heated to 50 ℃ to 100 ℃ before the partially unsaturated hydrocarbon gas is reacted.

16. The method for deoxidizing unsaturated hydrocarbon gas as claimed in any one of claims 6 to 15, wherein said method for deoxidizing unsaturated hydrocarbon gas comprises:

step S30, reacting the third deoxidized unsaturated hydrocarbon gas obtained in step S20c under a fourth catalyst to obtain a fourth deoxidized unsaturated hydrocarbon gas.

17. The unsaturated hydrocarbon gas deoxidation method claimed in claim 16, wherein in said step S30, the reaction temperature can be controlled at 180 ℃ to 500 ℃; preferably, the reaction temperature can be controlled between 195 ℃ and 425 ℃.

18. The method for deoxidizing unsaturated hydrocarbon gas as set forth in claim 16,

the initial catalyst is one or more of molybdenum series, copper series, nickel series, manganese series, platinum series and palladium series reductive deoxidation catalysts;

the first catalyst may include a platinum-based and/or palladium-based reductive deoxygenation catalyst;

the second catalyst may include one or more of platinum-series, molybdenum-series, copper-series, nickel-series, and manganese-series reductive deoxygenation catalysts;

the third catalyst may include one or more of a molybdenum-based, copper-based, nickel-based, and manganese-based reductive deoxygenation catalyst;

the fourth catalyst may include one or more of a molybdenum-based, copper-based, nickel-based, and manganese-based reductive deoxygenation catalyst.

19. The method for deoxygenating of an unsaturated hydrocarbon gas of any one of claims 1-15, wherein the unsaturated hydrocarbon gas comprises one or more of unsaturated hydrocarbon gases having 2-5 carbon atoms.

20. The method for deoxidizing unsaturated hydrocarbon gas as claimed in any one of claims 1 to 15, wherein the oxygen content in the unsaturated hydrocarbon gas to be deoxidized is 0.2% to 12% by weight, and the oxygen content in the unsaturated hydrocarbon gas after being deoxidized is 2000ppm or less.

Technical Field

The invention relates to the technical field of deoxidation, in particular to a deoxidation method for unsaturated hydrocarbon gas.

Background

Oxygen-containing organic hydrocarbon gas is a common gas in the processes of chemical production, storage and transportation at present, and oxygen-containing unsaturated hydrocarbon gas is taken as an example, and the oxygen content is high, so that the explosion risk is often caused. Therefore, in order to reduce the risk of explosion, recycle the oxygen-containing organic hydrocarbon gas and ensure that the oxygen-containing organic hydrocarbon gas meets the emission requirement, the oxygen-containing organic hydrocarbon gas needs to be deoxidized to reduce the oxygen content.

At present, the deoxidation technology mainly comprises physical pressure swing adsorption deoxidation, chemical adsorption deoxidation, activated carbon combustion deoxidation, catalytic combustion deoxidation and catalytic oxidation deoxidation. Wherein: the physical pressure swing adsorption deoxidation and the chemical adsorption deoxidation have small loads and poor deoxidation effect; the combustion deoxidization temperature of the activated carbon is high, and the energy consumption is high; catalytic combustion deoxidation technology mostly needs to add reducing gas such as H₂. The current catalytic oxidation deoxidation technology is mainly used for removing oxygen in methane-containing gases such as coal bed gas, landfill gas and the like, so that the current catalytic oxidation deoxidation technology is applied to deoxidation of unsaturated hydrocarbon gas, and particularly when the oxygen content in the unsaturated hydrocarbon gas is high, such as the oxygen content is 0.2-12 wt%, the deoxidation effect is poor.

Disclosure of Invention

The invention aims to solve the problem of poor deoxidation effect when the oxygen content in unsaturated hydrocarbon gas is high in the prior art, and provides a method for deoxidizing unsaturated hydrocarbon gas.

In order to achieve the above object, an aspect of the present invention provides a method for deoxidizing an unsaturated hydrocarbon gas, including:

step S10, reacting part of unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxidized under the action of an initial catalyst to obtain deoxidized unsaturated hydrocarbon gas;

step S20, dividing the remaining unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxygenated into a plurality of parts, so that each part of the unsaturated hydrocarbon gas to be deoxygenated and the deoxygenated unsaturated hydrocarbon gas obtained in the previous step react together under the action of a corresponding catalyst to obtain the deoxygenated unsaturated hydrocarbon gas.

According to the technical scheme, the raw material gas is divided into a plurality of parts, one part of the raw material gas is firstly used for generating the deoxidized unsaturated hydrocarbon gas, and then each remaining part of the raw material gas and the deoxidized unsaturated hydrocarbon gas obtained in the previous step are jointly reacted under the action of the corresponding catalyst, so that oxygen contained in the unsaturated hydrocarbon gas can be effectively removed, the deoxidizing efficiency is greatly improved, and meanwhile, the deoxidizing reaction can release heat, so that the reaction is gradually carried out, the temperature during deoxidizing can be well controlled, the phenomenon of carbon deposition on the catalyst is greatly reduced, and the service life of the catalyst is prolonged.

Preferably, in the step S10, the reaction amount of the partially unsaturated hydrocarbon gas is 2% to 40% of the total amount of the unsaturated hydrocarbon gas to be deoxygenated.

Preferably, the reaction amount of the partially unsaturated hydrocarbon gas is 5% to 30% of the total amount of the unsaturated hydrocarbon gas to be deoxygenated.

Preferably, in the step S20, the remaining unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxygenated is divided into 2 to 20 fractions, and preferably, the remaining unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxygenated is divided into 3 to 10 fractions.

Preferably, in the step S20, the reaction temperature can be controlled at 50 to 580 ℃ per part of the reaction, and preferably, the reaction temperature can be controlled at 60 to 450 ℃; and/or

In the step S20, the reaction space velocity is controlled at 500 per part of reaction^-1-45000h^-1(ii) a Preferably, the reaction space velocity is controlled at 1000^-1-22000h^-1。

Preferably, the remaining unsaturated hydrocarbon gas is divided into a first part of unsaturated hydrocarbon gas, a second part of unsaturated hydrocarbon gas and a third part of unsaturated hydrocarbon gas; the step S20 includes:

step S20a, reacting the first part of unsaturated hydrocarbon gas and the deoxidized unsaturated hydrocarbon gas obtained in step S10 together under the action of a first catalyst to obtain a first deoxidized unsaturated hydrocarbon gas;

step S20b, reacting the second part of unsaturated hydrocarbon gas and the first deoxidized unsaturated hydrocarbon gas obtained in step S20a together under the action of a second catalyst to obtain a second deoxidized unsaturated hydrocarbon gas;

step S20c, reacting the third part of unsaturated hydrocarbon gas and the second deoxidized unsaturated hydrocarbon gas obtained in step S20b together under the action of a third catalyst to obtain a third deoxidized unsaturated hydrocarbon gas.

Preferably, in the step S20a, the reaction amount of the first part of unsaturated hydrocarbon gas is 10% to 30% of the total amount of the unsaturated hydrocarbon gas to be deoxygenated;

in the step S20b, the reaction amount of the second part of unsaturated hydrocarbon gas is 15 to 40% of the total amount of the unsaturated hydrocarbon gas to be deoxygenated;

in the step S20c, the reaction amount of the third part of the unsaturated hydrocarbon gas is 15% to 30% of the total amount of the unsaturated hydrocarbon gas to be deoxygenated.

Preferably, in the step S20a, the reaction temperature can be controlled at 40-200 ℃; preferably, the reaction temperature can be controlled between 60 ℃ and 185 ℃.

Preferably, in the step S20a, the reaction space velocity is controlled at 500^-1-45000h^-1(ii) a Preferably, the reaction space velocity is controlled at 1000^-1-22000h^-1。

Preferably, in the step S20b, the reaction temperature can be controlled at 100 ℃ ℃, -380 ℃, and preferably, the reaction temperature can be controlled at 145 ℃ to 325 ℃.

Preferably, in the step S20b, the reaction space velocity is controlled at 500^-1-45000h^-1(ii) a Preferably, the reaction space velocity is controlled at 1200^-1-22000h^-1。

Preferably, in the step S20c, the reaction temperature can be controlled at 175 ℃ to 580 ℃; preferably, the reaction temperature can be controlled between 225 ℃ and 450 ℃.

Preferably, in the step S20c, the reaction space velocity is controlled at 500h^-1-45000h^-1(ii) a Preferably, the reaction space velocity is controlled at 1500^-1-22000h^-1。

Preferably, in the step S10, the reaction temperature can be controlled at 30 ℃ to 200 ℃; preferably, the reaction temperature can be controlled between 40 ℃ and 180 ℃.

Preferably, in the step S10, the partially unsaturated hydrocarbon gas is heated to 30 ℃ to 160 ℃, preferably, the partially unsaturated hydrocarbon gas is heated to 50 ℃ to 100 ℃ before the partially unsaturated hydrocarbon gas is reacted.

Preferably, the method for deoxidizing unsaturated hydrocarbon gas includes:

step S30, reacting the third deoxidized unsaturated hydrocarbon gas obtained in step S20c under a fourth catalyst to obtain a fourth deoxidized unsaturated hydrocarbon gas.

Preferably, in the step S30, the reaction temperature can be controlled at 180 ℃ to 500 ℃; preferably, the reaction temperature can be controlled between 195 ℃ and 425 ℃.

Preferably, the initial catalyst is one or more of molybdenum-series, copper-series, nickel-series, manganese-series, platinum-series and palladium-series reductive deoxidation catalysts;

the first catalyst may include a platinum-based and/or palladium-based reductive deoxygenation catalyst;

the second catalyst may include one or more of a molybdenum-based, copper-based, nickel-based, and manganese-based reductive deoxygenation catalyst;

the third catalyst may include one or more of platinum-series, molybdenum-series, copper-series, nickel-series, and manganese-series reductive deoxygenation catalysts;

the fourth catalyst may include one or more of a molybdenum-based, copper-based, nickel-based, and manganese-based reductive deoxygenation catalyst.

Preferably, the unsaturated hydrocarbon gas includes one or more of unsaturated hydrocarbon gases having 2 to 5 carbon atoms.

Preferably, the oxygen content in the unsaturated hydrocarbon gas to be deoxygenated is 0.2% to 12% by weight, and the oxygen content in the unsaturated hydrocarbon gas after deoxygenation is 2000ppm or less.

Drawings

Fig. 1 is a schematic sectional view showing a preferred deoxygenation device for an unsaturated hydrocarbon gas, which realizes the deoxygenation method for an unsaturated hydrocarbon gas according to the preferred embodiment of the present invention.

Description of the reference numerals

A deoxidation apparatus for 10-unsaturated hydrocarbon gas; 12-a housing; 120-main feed inlet; 122-a discharge outlet; 124-auxiliary feed inlet; 130-flap plate turning; 132-an inlet; 134-an outlet; 140-a containment chamber; 141-a first channel; 142-a first catalyst layer; 143-a second channel; 144-a partition plate; 145-a second gap; 146-a spacer plate; 147-a third gap; 148-a first gap; 16-a first ceramic ball layer; 18-an oxygen detector; 20-a second catalyst layer; 22-a third catalyst layer; 24-a second ceramic ball layer; 260-heat exchanger inlet; 262-heat exchanger outlet; 28-pressure detection alarm.

Detailed Description

In the present invention, the use of directional terms such as "upper, lower, left and right" in the absence of a contrary explanation generally means that the directions shown in the drawings and the practical application are considered to be the same, and "inner and outer" mean the inner and outer of the outline of the component.

The invention provides a method for deoxidizing unsaturated hydrocarbon gas, which comprises the following steps: step S10, reacting a part of the unsaturated hydrocarbon gas to be deoxygenated under the action of an initial catalyst to obtain a deoxygenated unsaturated hydrocarbon gas, wherein the unsaturated hydrocarbon gas may include one or more of unsaturated hydrocarbon gases having 2 to 5 carbon atoms, such as ethylene, propylene, butylene, and acetylene, and step S20, dividing the remaining unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxygenated into a plurality of parts, so that each part of the unsaturated hydrocarbon gas to be deoxygenated and the deoxygenated unsaturated hydrocarbon gas obtained in the previous step are reacted together under the action of a corresponding catalyst to obtain the deoxygenated unsaturated hydrocarbon gas. The raw material gas is divided into several parts, and one part of the raw material gas is firstly subjected to deoxidation reaction under the promotion action of an initial catalyst, namely, unsaturated hydrocarbon gas in the raw material gas and oxygen contained in the raw material gas are subjected to reaction to obtain deoxidized unsaturated hydrocarbon gas, wherein the reacted unsaturated hydrocarbon gas can still contain oxygen; and carrying out deoxidation reaction on each residual part and the deoxidized unsaturated hydrocarbon gas obtained in the previous step under the action of a corresponding catalyst to obtain the deoxidized unsaturated hydrocarbon gas. The raw material gas is divided into a plurality of parts, so that one part of the raw material gas firstly generates deoxidized unsaturated hydrocarbon gas, and then each remaining part and the deoxidized unsaturated hydrocarbon gas obtained in the previous step react together under the action of a corresponding catalyst, thereby not only effectively removing oxygen contained in the unsaturated hydrocarbon gas, but also greatly improving the deoxidizing efficiency.

In the step S10 and the step S20, the catalyst may be one or more of a molybdenum-based reductive deoxygenation catalyst, a copper-based reductive deoxygenation catalyst, a nickel-based reductive deoxygenation catalyst, a manganese-based reductive deoxygenation catalyst, a platinum-based reductive deoxygenation catalyst, and it should be noted that, taking the molybdenum-based reductive deoxygenation catalyst as an example, the molybdenum-based reductive deoxygenation catalyst includes a carrier and an active component molybdenum supported on the carrier, and the rest of the catalysts are the same and all include a carrier and a corresponding active component metal supported on the carrier, and details are not repeated here. Preferably, in the step S10, the catalyst may be selected from platinum group and/or palladium group catalysts; in the step S20, the catalyst may be one or more of platinum-based, palladium-based, molybdenum-based, copper-based, nickel-based, and manganese-based reductive deoxidation catalysts.

In order to achieve both the oxygen removing effect and the oxygen removing efficiency, the remaining unsaturated hydrocarbon gas may be divided into a first part of unsaturated hydrocarbon gas, a second part of unsaturated hydrocarbon gas, and a third part of unsaturated hydrocarbon gas, that is, the remaining unsaturated hydrocarbon gas in the step S20 may be divided into three parts.

In order to allow the reaction to sufficiently proceed, in the step S20, the remaining unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxygenated may be divided into 2 to 20 fractions, and preferably, the remaining unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxygenated may be divided into 3 to 10 fractions.

In the step S20, the reaction temperature can be controlled at 50 to 580 ℃ per part of the reaction, preferably, the reaction temperature can be controlled at 60 to 450 ℃; in addition, in the step S20, the reaction space velocity is controlled to 500 per part of the reaction^-1-45000h^-1(ii) a Preferably, the reaction space velocity is controlled at 1000^-1-22000h^-1。

Further preferably, the step S20 may include the following three parts: s20a, reacting the first part of unsaturated hydrocarbon gas and the deoxidized unsaturated hydrocarbon gas obtained in the step S10 under the action of a first catalyst to obtain a first deoxidized unsaturated hydrocarbon gas, preferably, reacting the first part of unsaturated hydrocarbon gas and the deoxidized unsaturated hydrocarbon gas obtained in the step S10 together under the action of a first catalyst after the first part of unsaturated hydrocarbon gas and the deoxidized unsaturated hydrocarbon gas are uniformly mixed, wherein the first catalyst may include a platinum-based catalyst and/or a palladium-based catalyst; s20b, reacting the second part of unsaturated hydrocarbon gas and the first deoxidized unsaturated hydrocarbon gas obtained in step S20a together under the action of a second catalyst to obtain a second deoxidized unsaturated hydrocarbon gas, preferably, reacting the second part of unsaturated hydrocarbon gas and the deoxidized unsaturated hydrocarbon gas obtained in step S20a together under the action of a second catalyst after being uniformly mixed, wherein the second catalyst may include one or more of molybdenum-based, copper-based, nickel-based and manganese-based catalysts; s20c, reacting the third part of unsaturated hydrocarbon gas and the second deoxidized unsaturated hydrocarbon gas obtained in step S20b together under the action of a third catalyst to obtain a third deoxidized unsaturated hydrocarbon gas, preferably, reacting the third part of unsaturated hydrocarbon gas and the deoxidized unsaturated hydrocarbon gas obtained in step S20b together under the action of a third catalyst after being mixed uniformly, wherein the third catalyst may include one or more of molybdenum-based, copper-based, nickel-based, and manganese-based reductive deoxidation catalysts.

In order to improve the oxygen removing effect, in step S10, the reaction amount of the partially unsaturated hydrocarbon gas is preferably 2% to 40% of the total amount of the unsaturated hydrocarbon gas to be deoxygenated, that is, 2% to 40% of the total amount of the unsaturated hydrocarbon gas may be reacted under the action of the initial catalyst to obtain the deoxygenated unsaturated hydrocarbon gas. Preferably, the reaction amount of the partially unsaturated hydrocarbon gas is 5% to 30% of the total amount of the unsaturated hydrocarbon gas to be deoxygenated.

In the step S10, the reaction temperature can be controlled between 30 ℃ and 200 ℃; preferably, the reaction temperature can be controlled to be 40-180 ℃, so that the deoxidation reaction can be stably and efficiently carried out, and the phenomenon of carbon deposition on the catalyst is greatly reduced. It is understood that the reaction is carried out stepwise, and the reaction temperature can be controlled within a certain temperature range.

In order to increase the reaction efficiency, the partially unsaturated hydrocarbon gas is heated to 30 ℃ to 160 ℃ in the step S10, and preferably, the partially unsaturated hydrocarbon gas is heated to 50 ℃ to 100 ℃ before the partially unsaturated hydrocarbon gas is reacted.

In addition, in the step S10, the reaction pressure is preferably controlled to be 5MPa or less, thereby allowing the reaction to be stably and safely carried out.

In said step S10, the reaction space velocity is preferably controlled at 500^-1-50000h^-1Thereby taking reaction efficiency and reaction effect into consideration, and further, the reaction space velocity is preferably controlled to be 800^-1-25000h^-1Further, the reaction space velocity is preferably controlled to 1500^-1-10000h^-1。

In the step S20a, the reaction amount of the first part of the unsaturated hydrocarbon gas is preferably 2% to 40% of the total amount of the unsaturated hydrocarbon gas to be deoxygenated, that is, 10% to 30% of the total amount of the unsaturated hydrocarbon gas is preferably reacted as the first part of the unsaturated hydrocarbon gas together with the deoxygenated unsaturated hydrocarbon gas obtained in the step S10 under the action of a first catalyst.

In addition, in the step S20a, the reaction temperature can be controlled at 40-200 ℃; preferably, the reaction temperature can be controlled to be 60-185 ℃, so that the reaction can be stably and efficiently carried out, and the carbon deposition phenomenon of the catalyst is further reduced.

In the step S20a, the reaction pressure is preferably controlled to be 5MPa or less, thereby allowing the reaction to proceed stably and safely.

In the step S20a, the reaction space velocity is controlled at 500^-1-45000h^-1. Further, the reaction space velocity is preferably controlled to 1000^-1-22000h^-1Further, the reaction space velocity is preferably controlled to 1800^-1-10000h^-1. Thus, control of the reaction temperature can be facilitated.

In the step S20b, the reaction amount of the second part of unsaturated hydrocarbon gas is preferably 15% to 40% of the total amount of the unsaturated hydrocarbon gas to be deoxygenated, that is, it is preferable that 15% to 40% of the total amount of unsaturated hydrocarbon gas as the second part of unsaturated hydrocarbon gas is reacted together with the deoxygenated unsaturated hydrocarbon gas obtained in the step S20a under the action of a second catalyst.

In addition, in the step S20b, the reaction temperature can be controlled at 380 ℃ of 100, preferably, the reaction temperature can be controlled at 145-325 ℃, so that the reaction can be stably and efficiently performed, and the carbon deposition phenomenon of the catalyst is further reduced. The reaction is carried out step by step, and the temperature can be controlled within a certain range.

In the step S20b, the reaction pressure is preferably controlled to be 5MPa or less, thereby allowing the reaction to proceed stably and safely.

In the step S20b, the reaction space velocity is preferably controlled to 500^-1-45000h^-1. Further, the reaction space velocity is preferably controlled to 1200^-1-22000h^-1Further, the reaction space velocity is preferably controlled to 2000^-1-10000h^-1。

In the step S20c, the reaction amount of the third part of the unsaturated hydrocarbon gas is preferably 15% to 30% of the total amount of the unsaturated hydrocarbon gas to be deoxygenated, that is, it is preferable that 15% to 30% of the total amount of the unsaturated hydrocarbon gas as the third part of the unsaturated hydrocarbon gas is reacted together with the deoxygenated unsaturated hydrocarbon gas obtained in the step S20b under the action of a third catalyst.

In addition, in the step S20c, the reaction temperature can be controlled to 175-580 ℃, so that the reaction can be performed with high efficiency, and the carbon deposition phenomenon of the catalyst is further reduced. Preferably, the reaction temperature can be controlled between 225 ℃ and 450 ℃.

In the step S20c, the reaction pressure is preferably controlled to be 5MPa or less, thereby allowing the reaction to proceed stably and safely.

In the step S20c, the reaction space velocity is controlled at 500^-1-45000h^-1. Further, the reaction space velocity is preferably controlled to 1500^-1-22000h^-1Further, the space velocity of the reaction is preferably controlled to 2500^-1-10000h^-1。

In order to further increase the deoxidation rate, the method for deoxidizing unsaturated hydrocarbon gas preferably includes: step S30, reacting the third deoxidized unsaturated hydrocarbon gas obtained in step S20c under a fourth catalyst to obtain a fourth deoxidized unsaturated hydrocarbon gas. Wherein the fourth catalyst may include one or more of molybdenum-based, copper-based, nickel-based, and manganese-based reductive deoxygenation catalysts.

In the step S30, the reaction temperature can be controlled between 180 ℃ and 500 ℃; preferably, the reaction temperature can be controlled to be 195 ℃ -425 ℃, so that the deoxidation reaction is stably and efficiently carried out, and the phenomenon of carbon deposition on the catalyst is greatly reduced.

In addition, in the step S30, the reaction pressure is preferably controlled to be 5MPa or less, thereby allowing the reaction to be stably and safely carried out.

The oxygen content in the unsaturated hydrocarbon gas with the oxygen content of 0.2 to 12 weight percent can be reduced to below 2000ppm by utilizing the deoxidation method provided by the invention. In addition, when the oxygen content in the finally obtained deoxidized unsaturated hydrocarbon gas is more than 2000ppm, the catalyst can be regenerated, wherein the method for regenerating the catalyst can be various and can be selected according to actual requirements, for example, carbon can be burnt in an oxygen atmosphere with a certain concentration.

It should be noted that the whole reaction process is preferably carried out under an inert gas atmosphere such as a nitrogen gas atmosphere.

The method for deoxidizing unsaturated hydrocarbon gas provided by the present invention can be realized by using the deoxidizing device for unsaturated hydrocarbon gas shown in fig. 1.

The deoxygenator device 10 for unsaturated hydrocarbon gas comprises a housing 12, wherein the housing 12 is provided with a main feed opening 120 for feeding the unsaturated hydrocarbon gas containing oxygen and a discharge opening 122 for discharging the deoxygenated unsaturated hydrocarbon gas, respectively, and it is understood that the deoxygenated unsaturated hydrocarbon gas can be discharged from the discharge opening 122, wherein the main feed opening 120 is located above the discharge opening 122, specifically, the main feed opening 120 can be arranged at the top of the housing 12, and the discharge opening 122 can be arranged at the bottom of the housing 12; the deoxidation apparatus 10 for unsaturated hydrocarbon gas further comprises a reaction unit which is disposed in the housing 12 and is disposed between the main feed opening 120 and the discharge opening 122, the reaction unit comprises a first reaction unit which comprises a reaction bed 14, the reaction bed 14 has a housing chamber 140, a first catalyst layer 142 which promotes the reaction of unsaturated hydrocarbon gas and oxygen is disposed in the housing chamber 140, that is, under the action of the first catalyst layer 142, the unsaturated hydrocarbon gas and oxygen can be reacted to remove oxygen contained in the unsaturated hydrocarbon, the housing chamber 140 has an inlet 132 through which the unsaturated hydrocarbon gas containing oxygen enters and an outlet 134 through which the unsaturated hydrocarbon gas after deoxidation is discharged, wherein the kind of the catalyst in the first catalyst layer 142 is not particularly limited as long as the reaction of the unsaturated hydrocarbon gas and oxygen can be promoted, for example, one or more of molybdenum-based, copper-based, nickel-based, manganese-based, platinum-based, palladium-based reductive deoxygenation catalysts may be selected, and it is noted that the unsaturated hydrocarbon gas containing oxygen gas introduced from the main feed port 120 is introduced into the accommodating chamber 140 through the inlet 132, and reacts to remove oxygen by the first catalyst layer 142. By providing the first catalyst layer 142 in the accommodation chamber 140, the unsaturated hydrocarbon gas and the oxygen gas can be promoted to react, thereby achieving the purpose of removing the oxygen gas from the unsaturated hydrocarbon gas. The unsaturated hydrocarbon gas may include one or more of ethylene, propylene, butylene, and acetylene, among others.

In order to further improve the oxygen removal effect and the oxygen removal efficiency, the first reaction unit may include a plurality of, for example, three reaction beds 14 distributed in the height direction of the housing 12. Preferably, a plurality of reaction beds 14 are connected in series with each other, and it is understood that in two adjacent reaction beds 14, the outlet 134 of the reaction bed 14 located at the upper layer is connected with the inlet 132 of the reaction bed 14 located at the lower layer, for the sake of simple overall structure, the outlet 134 of the reaction bed 14 located at the upper layer and the inlet 132 of the reaction bed 14 located at the lower layer may be the same port, and in addition, the inlet 132 of the reaction bed 14 located at the topmost layer is connected with the main feed inlet 120. Taking three reaction bed bodies 14 as an example, the first reaction bed body, the second reaction bed body and the third reaction bed body are arranged from top to bottom in sequence, so that after the unsaturated hydrocarbon gas containing oxygen enters the inlet 132 of the first reaction bed body from the main feed inlet 120, the unsaturated hydrocarbon gas is reacted in the first reaction bed body to obtain deoxidized unsaturated hydrocarbon gas, and then the deoxidized first unsaturated hydrocarbon gas can be discharged from the outlet 134 of the first reaction bed body; the deoxidized first unsaturated hydrocarbon gas enters the second reaction bed body from the inlet 132 of the second reaction bed body to react to obtain deoxidized second unsaturated hydrocarbon gas, and then the deoxidized second unsaturated hydrocarbon gas is discharged from the outlet 134 of the second reaction bed body; the deoxidized second unsaturated hydrocarbon gas enters the third reaction bed body from the inlet 132 of the third reaction bed body to react to obtain the deoxidized third unsaturated hydrocarbon gas, and then the deoxidized third unsaturated hydrocarbon gas is discharged from the outlet 134 of the third reaction bed body.

As shown in fig. 1, a plurality of partition plates 144 may be provided at intervals in the height direction of the shell 12, adjacent partition plates 144 defining respective reaction beds 14, it being understood that the accommodation chambers 140 are defined between respective adjacent partition plates 144, the first catalyst layers 142 are provided between respective adjacent partition plates 144, the partition plates 144 being provided with openings, wherein: of the two adjacent partition plates 144, the opening of the partition plate 144 located above is formed as the inlet 132 of the corresponding reaction bed 14, and the opening of the partition plate 144 located below is formed as the outlet 134 of the corresponding reaction bed 14. Wherein, preferably, the outer circumference of the partition plate 144 is in contact with the inner wall of the housing 12.

Partition plates 146 may be provided in the accommodation chambers 140, the partition plates 146 preferably being capable of supporting the first catalyst layers 142, as shown in fig. 1, the partition plates 146 may be provided below the respective first catalyst layers 142, first gaps 148 through which gas, that is, unsaturated hydrocarbon gas, passes may be formed between outer peripheries of the partition plates 146 and inner walls of the housing 12, and first passages 141 through which gas passes may be formed between the partition plates 146 and the lower partition plate 144 of the adjacent two partition plates 144, which are in communication with the first gaps 148, such that unsaturated hydrocarbon gas obtained by the deoxidation reaction performed by the first catalyst layers 142 flows through the first catalyst layers 142, enters the first passages 141 through the first gaps 148, and finally, the unsaturated hydrocarbon gas is discharged from the openings of the lower partition plates 144, that is, the outlets 134 of the respective accommodation chambers 140. It is to be understood that the first catalyst layer 146 may define between the upper separation plate 144 and the corresponding separation plate 146 of the adjacent two separation plates 144.

In addition, a third gap 147 through which a gas, i.e., an unsaturated hydrocarbon gas, passes may be provided between the outer periphery of the first catalyst layer 142 and the inner wall of the housing 12, and the unsaturated hydrocarbon gas passes through the third gap 147 after reacting in the first catalyst layer 142, and then enters the first passage 141 through the first gap 148. By providing the third gap 147, the gas can be guided, so that the gas can enter the first channel 141 better and more conveniently.

In order to allow the unsaturated hydrocarbon gas to better react with oxygen, second channels 143 may be provided on the first catalyst layer 142 for passing gas, so that the unsaturated hydrocarbon gas may better contact the catalyst in the first catalyst layer 142, thereby allowing the unsaturated hydrocarbon gas to better react with oxygen contained in the unsaturated hydrocarbon gas.

It will be appreciated that gas may flow in a horizontal direction through the second channels 143, for example in a radial direction of the housing 12, before entering the respective third gaps 147 and passing through the respective first gaps 148 into the first channels 141.

Preferably, the main feed port 120 may be connected to the inlet 132 of the topmost accommodating chamber 140, it is understood that the oxygen-containing unsaturated hydrocarbon may be introduced into the topmost accommodating chamber 140 from the main feed port 120, the main feed port 120 may realize the feeding of the partially unsaturated hydrocarbon gas in step S10, a sub feed port 124 for the oxygen-containing unsaturated hydrocarbon gas may be provided on the housing 12 in communication with the corresponding accommodating chamber 140, the sub feed port 124 may realize the feeding of the remaining portions in step S20, and preferably, the sub feed port 124 may be provided at an end portion of the housing 12 near the first passage 141, so that the oxygen-containing unsaturated hydrocarbon gas introduced from the sub feed port 124 may be more conveniently introduced into the first passage 141; the reaction unit may include a second reaction unit disposed below the first reaction unit, the second reaction unit including a second catalyst layer 20 through which a gas, i.e., an unsaturated hydrocarbon gas, can pass, the second catalyst layer 20 being capable of promoting the unsaturated hydrocarbon gas in the gas to react with the oxygen. The oxygen removal efficiency can be improved by providing the sub feed port 124 and the second catalyst layer 20, and the oxygen removal effect is also greatly improved. The kind of the catalyst in the second catalyst layer 20 is not particularly limited as long as it can promote the reaction between the unsaturated hydrocarbon gas and the oxygen gas, and for example, one or more kinds of reductive deoxidation catalysts of molybdenum series, copper series, nickel series, manganese series, platinum series, and palladium series may be used.

Preferably, at the same position of the accommodating chamber 140, a plurality of auxiliary feed ports 124, which are respectively communicated with the corresponding same accommodating chamber 140 and are distributed at intervals along the circumferential direction of the casing 12, may be provided on the casing 12.

It will be appreciated that, as shown in fig. 1, for example, the unsaturated hydrocarbon gas to be deoxygenated may be divided into portions, a portion of which enters the topmost receiving chamber 140 from the main feed opening 120, and the rest of the oxygen-containing unsaturated hydrocarbon gas may be introduced into the corresponding receiving chambers 140 through the corresponding sub-inlet ports 120, respectively, and the oxygen-containing unsaturated hydrocarbon gas may be reacted in the topmost receiving chamber 140 to obtain deoxygenated unsaturated hydrocarbon gas (which may contain unremoved oxygen), it will be appreciated that step S10 may be implemented in the topmost receiving chamber 140, i.e., the first receiving chamber, and the resulting deoxygenated unsaturated hydrocarbon gas passes from the topmost first gap 148 into the topmost first passageway 141, and is mixed with the unsaturated hydrocarbon gas containing oxygen, i.e. the first part of unsaturated hydrocarbon gas, which enters from the corresponding auxiliary feed inlet 120, i.e. the topmost auxiliary feed inlet 120, to obtain a first mixed gas; the first mixed gas enters the accommodating chamber 140 adjacent to the topmost accommodating chamber 140, i.e. a second accommodating chamber, and is subjected to a deoxygenation reaction together to obtain deoxygenated unsaturated hydrocarbon gas, i.e. the step S20a is implemented in the second accommodating chamber, and is mixed with the oxygen-containing unsaturated hydrocarbon gas entering from the secondary feed port 120 communicated with the second accommodating chamber to obtain a second mixed gas; the second mixed gas enters a third accommodating chamber adjacent to the second accommodating chamber, and is subjected to a deoxidation reaction together to obtain a deoxidized unsaturated hydrocarbon gas, that is, the step S20b is implemented in the third accommodating chamber, and is mixed with the oxygen-containing unsaturated hydrocarbon gas entering from the auxiliary feed port 120 communicated with the third accommodating chamber to obtain a third mixed gas, and the third mixed gas flows through the second catalyst layer 20 to obtain the deoxidized unsaturated hydrocarbon gas, that is, the step S20c is implemented under the action of the second catalyst layer 20, so that the deoxidizing efficiency is improved, and the deoxidizing effect is greatly improved. It should also be noted that the multi-stage feeding can better control the temperature of the corresponding reaction bed 14, so that the catalyst is not easy to deposit carbon, and the service life of the catalyst is prolonged.

As shown in fig. 1, flow channels through which gas passes may be provided in the second catalyst layer 20, so that the unsaturated hydrocarbon gas passing through the flow channels may enter the second catalyst layer 20 to be sufficiently in contact with the catalyst in the second catalyst layer 20, whereby the catalytic effect may be further improved. In addition, a space may be formed between the outer periphery of the second catalyst layer 20 and the inner wall of the casing 12 for passing a gas, i.e., an unsaturated hydrocarbon gas.

In order to further enhance the oxygen removing effect, a third catalyst layer 22 may be provided below the second catalyst layer 20, so that the step S30 may be implemented by the third catalyst layer 22. The kind of the catalyst in the third catalyst layer 22 is not particularly limited as long as it can promote the reaction between the unsaturated hydrocarbon gas and the oxygen gas, and for example, one or more kinds of reductive deoxidation catalysts of molybdenum series, copper series, nickel series, manganese series, platinum series, and palladium series may be used.

In order to enable the steps to react at a more suitable temperature, the temperature of each catalyst layer may be controlled. In addition, the amount of unsaturated hydrocarbon gas introduced from the main feed port 120 and the sub feed port 124 may be controlled to control the pressure and space velocity at the reaction.

In addition, a second gas distribution body may be provided between the second catalyst layer 20 and the third catalyst layer 22, whereby the gas distribution may be made uniform, and the oxygen removal effect and the oxygen removal efficiency are further improved. Wherein, the gas distributor can comprise a second ceramic ball layer 24, and the unsaturated hydrocarbon gas can be uniformly distributed after passing through the second ceramic ball layer 24. The material of the second ceramic ball layer 24 is preferably alumina. In order to improve the oxygen removal effect, a plurality of second ceramic ball layers 24 may be provided, which are distributed along the height direction of the housing 12, and a plurality of support nets may be provided, which support the respective second ceramic ball layers 24, and finally, the deoxidized unsaturated hydrocarbon gas is discharged from the discharge opening 122.

As shown in fig. 1, a first distribution body, which may include the first ceramic ball layer 16 disposed in the first passage 141, may be disposed in the first passage 141 to uniformly distribute the gas, i.e., the unsaturated hydrocarbon gas, and thus the oxygen removal efficiency and the oxygen removal effect may be greatly improved. By providing the first ceramic ball layer 16, the material of the first ceramic ball layer 16 may preferably be alumina.

A second gap 145 may be provided between the outer periphery of the first ceramic ball layer 16 and the inner wall of the housing 12 for gas to pass through, so that the unsaturated hydrocarbon gas deoxidized by the corresponding first catalyst layer 142 may substantially pass through the corresponding first ceramic ball layer 16, thereby enabling better mixing with the unsaturated hydrocarbon gas containing oxygen introduced from the corresponding sub-feed port 124.

In addition, the turnover plate 130 connected with the spacing plate 146 at an angle can be arranged on the spacing plate 146, for example, the turnover plate 130 can be vertically arranged, and the turnover plate 130 can be positioned in the second gap 145 to prevent the gas from directly entering the first channel 141, so that the unsaturated hydrocarbon gas can stably flow through the first ceramic ball layer 16, the temperature of the reaction bed body 14 is not easily and rapidly increased, carbon deposition on the catalyst is not easily caused, and the oxygen removal effect is also improved.

The deoxygenator device 10 for unsaturated hydrocarbon gases may include an oxygen detector 18 in communication with the discharge opening 122, the oxygen detector 18 being configured to detect an oxygen content of the gas discharged through the discharge opening 122.

In addition, a plurality of air ducts communicated with the corresponding sub feed ports 124 and a flow controller connected to the air ducts may be provided at the sub feed ports 124, the flow controller being configured to control the flow rate of the gas entering the corresponding sub feed ports 124, and by controlling the amount of the unsaturated hydrocarbon gas containing oxygen entering from the sub feed ports 124, the corresponding first catalyst layer 142 may be controlled within a preset temperature range, so that the deoxidation reaction may be stably performed, and the carbon deposition on the catalyst may be greatly reduced. In addition, through setting up flow controller to can realize dynamic distribution, the temperature of each catalyst layer that can be timely adjusted has also improved the operating efficiency simultaneously.

It should be noted that the oxygen detector 18 and the flow controller may cooperate with each other, and the flow controller may control the flow rate of the gas entering the corresponding secondary feed port 124 according to the oxygen content of the gas detected by the oxygen detector 18, that is, the oxygen content of the unsaturated hydrocarbon gas. For example, when the oxygen content in the gas discharged from the discharge opening 122 is higher than a predetermined value, such as 2000ppm, the flow controller is adapted to adjust the flow rate of the gas entering the corresponding secondary feed opening 124 to promote the deoxidation reaction.

In order to more accurately control the temperature of the first catalyst layer 142, a pair of temperature sensors connected to the flow controller may be disposed in the accommodating chamber 140, and the pair of temperature sensors respectively detect the temperatures of the first catalyst layer 142 and the first ceramic ball layer 16 in the same accommodating chamber 140, and the flow controller controls the amount of the oxygen-containing unsaturated hydrocarbon gas introduced from the corresponding sub-feed port 124 if the temperature sensors detect that the temperature of the first catalyst layer 142 or the first ceramic ball layer 16 exceeds a preset temperature.

As shown in fig. 1, a heat exchanger capable of exchanging heat with the third catalyst layer 22 may be disposed in the third catalyst layer 22, so that the third catalyst layer 22 may be effectively cooled, carbon deposition on the catalyst of the third catalyst layer 22 is not likely to occur, and the service life of the catalyst is prolonged. The heat exchanger has a heat exchanger inlet 260 for the cooling medium to enter and a heat exchanger outlet 262 for the heat exchanged cooling medium to exit.

A pressure sensing alarm 28 may be provided on the housing 12, the pressure sensing alarm 28 being capable of sensing pressure within the housing 28, the pressure sensing alarm 28 being arranged to alarm when the pressure within the housing 14 is sensed to exceed a preset value.

When the unsaturated hydrocarbon gas having an oxygen content of 0.2 to 12 wt% is passed through the above-mentioned deoxidation apparatus 10 for unsaturated hydrocarbon gas, the oxygen content in the unsaturated hydrocarbon gas can be reduced to 2000ppm or less. In order to discharge the gas in the housing 12 in time, a safety valve may be provided on the top of the housing 12.

When the oxygen content in the unsaturated hydrocarbon gas discharged from the discharge opening 122 is greater than 2000ppm, the catalyst may be regenerated in situ, that is, oxygen with corresponding concentration is introduced into the main feed opening 120 and the auxiliary feed opening 124 to burn carbon.

In addition, in the start-up stage of the deoxygenation device 10, the unsaturated hydrocarbon gas containing oxygen is firstly introduced into the main feed port 120 at a low flow rate, and after the temperature of each catalyst layer reaches the corresponding preset temperature, the unsaturated hydrocarbon gas containing oxygen may be simultaneously introduced into the main feed port 120 and the auxiliary feed port 124.

To facilitate cleaning and maintenance of each reaction bed 14, a manhole 26 may be provided in the shell 12 in communication with a respective containment chamber 140.

It should be noted that the deoxidation reaction means that the unsaturated hydrocarbon gas and oxygen contained in the unsaturated hydrocarbon gas are reacted to remove oxygen from the unsaturated hydrocarbon gas.

The effects of the present invention will be further illustrated by examples.

Examples

Example 1 removal of oxygen from ethylene (oxygen content 6 wt%)

Deoxygenation was carried out in the following manner

Step S10, reacting 25% of unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxidized under the action of an initial catalyst to obtain deoxidized unsaturated hydrocarbon gas, wherein the initial catalyst is a palladium reductive deoxidizing catalyst, and the reaction temperature can be controlled at 100 ℃; the reaction space velocity is controlled to be 2500h^-1；

Dividing the remaining unsaturated gas into three parts;

step S20a, allowing the first part of unsaturated hydrocarbon gas and the deoxidized unsaturated hydrocarbon gas obtained in step S10 to jointly react under the action of a first catalyst to obtain a first deoxidized unsaturated hydrocarbon gas, wherein the reaction amount of the first part of unsaturated hydrocarbon gas is 20% of the total amount of the unsaturated hydrocarbon gas to be deoxidized, the first catalyst is a platinum-based reductive deoxidation catalyst, and the reaction temperature can be controlled at 150 ℃; the reaction space velocity is controlled to be 2500h^-1；

Step S20b, jointly reacting the second part of unsaturated hydrocarbon gas and the first deoxidized unsaturated hydrocarbon gas obtained in the step S20a under the action of a second catalyst to obtain a second deoxidized unsaturated hydrocarbon gas, wherein the reaction of the second part of unsaturated hydrocarbon gasThe amount of the second catalyst is 25 percent of the total amount of the unsaturated hydrocarbon gas to be deoxidized, the second catalyst is a molybdenum series reductive deoxidation catalyst, and the reaction temperature can be controlled at 280 ℃; the reaction space velocity is controlled to be 2500h^-1；

Step S20c, reacting the third part of unsaturated hydrocarbon gas and the second deoxidized unsaturated hydrocarbon gas obtained in step S20b together under the action of a third catalyst to obtain a third deoxidized unsaturated hydrocarbon gas, wherein the reaction amount of the third part of unsaturated hydrocarbon gas is 30% of the total amount of the unsaturated hydrocarbon gas to be deoxidized, the third catalyst is a nickel-based reductive deoxidation catalyst, and the reaction temperature can be controlled at 300 ℃; the reaction space velocity is controlled to be 2500h^-1。

Step S30, reacting the third deoxidized unsaturated hydrocarbon gas obtained in the step S20c under a fourth catalyst to obtain a fourth deoxidized unsaturated hydrocarbon gas, wherein the fourth catalyst is a molybdenum-based or nickel-based reductive deoxidizing catalyst (the mass ratio of nickel-based to manganese-based is 1:1), and the reaction temperature can be controlled at 350 ℃; the reaction space velocity is controlled to be 2500h^-1。

The oxygen content in the unsaturated hydrocarbon gas after the fourth deoxidation was detected to be 2000 ppm.

Example 2 removal of oxygen from propylene (oxygen content 6 wt%)

Deoxygenation was carried out in the following manner

Step S10, reacting 20% of unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxidized under the action of an initial catalyst to obtain deoxidized unsaturated hydrocarbon gas, wherein the initial catalyst is a platinum catalyst, and the reaction temperature can be controlled at 115 ℃; the reaction space velocity is controlled to be 3000h^-1；

Dividing the remaining unsaturated gas into three parts;

step S20a, jointly reacting the first part of unsaturated hydrocarbon gas and the deoxidized unsaturated hydrocarbon gas obtained in the step S10 under the action of a first catalyst to obtain a first deoxidized unsaturated hydrocarbon gas, wherein the reaction amount of the first part of unsaturated hydrocarbon gas is the reaction amount20% of the total amount of the unsaturated hydrocarbon gas to be deoxidized, wherein the first catalyst is a palladium reductive deoxidation catalyst, and the reaction temperature can be controlled at 150 ℃; the reaction space velocity is controlled to be 3000h^-1；

Step S20b, reacting the second part of unsaturated hydrocarbon gas and the first deoxidized unsaturated hydrocarbon gas obtained in step S20a together under the action of a second catalyst to obtain a second deoxidized unsaturated hydrocarbon gas, wherein the reaction amount of the second part of unsaturated hydrocarbon gas is 35% of the total amount of the unsaturated hydrocarbon gas to be deoxidized, the second catalyst is a molybdenum-based reductive deoxidation catalyst, and the reaction temperature can be controlled at 260 ℃; the reaction space velocity is controlled to be 3000h^-1；

Step S20c, reacting the third part of unsaturated hydrocarbon gas and the second deoxidized unsaturated hydrocarbon gas obtained in step S20b together under the action of a third catalyst to obtain a third deoxidized unsaturated hydrocarbon gas, wherein the reaction amount of the third part of unsaturated hydrocarbon gas is 25% of the total amount of the unsaturated hydrocarbon gas to be deoxidized, the third catalyst is a nickel-based reductive deoxidation catalyst, and the reaction temperature can be controlled at 330 ℃; the reaction space velocity is controlled to be 3000h^-1。

Step S30, reacting the third deoxidized unsaturated hydrocarbon gas obtained in the step S20c under a fourth catalyst to obtain a fourth deoxidized unsaturated hydrocarbon gas, wherein the fourth catalyst is a molybdenum-based reductive deoxidation catalyst, and the reaction temperature can be controlled at 380 ℃; the reaction space velocity is controlled to be 3000h^-1。

The oxygen content in the fourth deoxygenated unsaturated hydrocarbon gas was determined to be 1300 ppm.

Example 3 removal of oxygen from acetylene (oxygen content 6 wt%)

Deoxygenation was carried out in the following manner

Step S10, reacting 14% of unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxidized under the action of an initial catalyst to obtain deoxidized unsaturated hydrocarbon gas, wherein the initial catalyst is a palladium reductive deoxidizing catalyst, and reactingThe temperature can be controlled at 120 ℃; the reaction space velocity is controlled at 6000h^-1；

Dividing the remaining unsaturated gas into three parts;

step S20a, allowing the first part of unsaturated hydrocarbon gas and the deoxidized unsaturated hydrocarbon gas obtained in step S10 to react together under the action of a first catalyst to obtain a first deoxidized unsaturated hydrocarbon gas, wherein the reaction amount of the first part of unsaturated hydrocarbon gas is 26% of the total amount of the unsaturated hydrocarbon gas to be deoxidized, the first catalyst is a palladium-based reductive deoxidation catalyst, and the reaction temperature can be controlled at 165 ℃; the reaction space velocity is controlled at 6000h^-1；

Step S20b, reacting the second part of unsaturated hydrocarbon gas and the first deoxidized unsaturated hydrocarbon gas obtained in step S20a together under the action of a second catalyst to obtain a second deoxidized unsaturated hydrocarbon gas, wherein the reaction amount of the second part of unsaturated hydrocarbon gas is 35% of the total amount of the unsaturated hydrocarbon gas to be deoxidized, the second catalyst is a platinum-based reductive deoxidation catalyst, and the reaction temperature can be controlled at 260 ℃; the reaction space velocity is controlled at 6000h^-1；

Step S20c, reacting the third part of unsaturated hydrocarbon gas and the second deoxidized unsaturated hydrocarbon gas obtained in step S20b together under the action of a third catalyst to obtain a third deoxidized unsaturated hydrocarbon gas, wherein the reaction amount of the third part of unsaturated hydrocarbon gas is 25% of the total amount of the unsaturated hydrocarbon gas to be deoxidized, the third catalyst is a molybdenum-based reductive deoxidation catalyst, and the reaction temperature can be controlled at 350 ℃; the reaction space velocity is controlled at 6000h^-1。

Step S30, reacting the third deoxidized unsaturated hydrocarbon gas obtained in the step S20c under a fourth catalyst to obtain a fourth deoxidized unsaturated hydrocarbon gas, wherein the fourth catalyst is a molybdenum catalyst, and the reaction temperature can be controlled at 420 ℃; the reaction space velocity is controlled at 6000h^-1。

The oxygen content in the unsaturated hydrocarbon gas after the fourth deoxidation was detected to be 500 ppm.

Example 4 removal of oxygen from propyne (oxygen content 12 wt%)

Deoxygenation was carried out in the following manner

Step S10, reacting 14% of unsaturated hydrocarbon gas in the unsaturated hydrocarbon gas to be deoxidized under the action of an initial catalyst to obtain deoxidized unsaturated hydrocarbon gas, wherein the initial catalyst is a platinum catalyst, and the reaction temperature can be controlled at 140 ℃; the reaction space velocity is controlled at 4000h^-1；

Dividing the remaining unsaturated gas into three parts;

step S20a, allowing the first part of unsaturated hydrocarbon gas and the deoxidized unsaturated hydrocarbon gas obtained in step S10 to react together under the action of a first catalyst to obtain a first deoxidized unsaturated hydrocarbon gas, wherein the reaction amount of the first part of unsaturated hydrocarbon gas is 20% of the total amount of the unsaturated hydrocarbon gas to be deoxidized, the first catalyst is a palladium-based reductive deoxidation catalyst, and the reaction temperature can be controlled at 180 ℃; the reaction space velocity is controlled at 4000h^-1；

Step S20b, reacting the second part of unsaturated hydrocarbon gas and the first deoxidized unsaturated hydrocarbon gas obtained in step S20a together under the action of a second catalyst to obtain a second deoxidized unsaturated hydrocarbon gas, wherein the reaction amount of the second part of unsaturated hydrocarbon gas is 38% of the total amount of the unsaturated hydrocarbon gas to be deoxidized, the second catalyst is a palladium-based reductive deoxidation catalyst, and the reaction temperature can be controlled at 220 ℃; the reaction space velocity is controlled at 4000h^-1；

Step S20c, reacting the third part of unsaturated hydrocarbon gas and the second deoxidized unsaturated hydrocarbon gas obtained in the step S20b together under the action of a third catalyst to obtain a third deoxidized unsaturated hydrocarbon gas, wherein the reaction amount of the third part of unsaturated hydrocarbon gas is 28% of the total amount of the unsaturated hydrocarbon gas to be deoxidized, the third catalyst is a nickel-based or manganese-based reductive deoxidation catalyst (the mass ratio of nickel to manganese is 1:1), and the reaction temperature can be controlled at 350 DEG C(ii) a The reaction space velocity is controlled at 4000h^-1。

Step S30, reacting the third deoxidized unsaturated hydrocarbon gas obtained in the step S20c under a fourth catalyst to obtain a fourth deoxidized unsaturated hydrocarbon gas, wherein the fourth catalyst is a nickel-based catalyst or a manganese-based catalyst, and the reaction temperature can be controlled at 420 ℃; the reaction space velocity is controlled at 4000h^-1。

The oxygen content in the unsaturated hydrocarbon gas after the fourth deoxidation was detected to be 900 ppm.

The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, numerous simple modifications can be made to the technical solution of the invention, including combinations of the individual specific technical features in any suitable way. The invention is not described in detail in order to avoid unnecessary repetition. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.