Method for preparing polymer grade low-carbon olefin through separation of methanol pyrolysis gas

• US 8,853,485 B2
• Filed: 07/27/2007
• Issued: 10/07/2014
• Est. Priority Date: 07/27/2007
• Status: Active Grant

• Current Assignee: China MTO Limited, Daqing Petrochemical Engineering Co., Ltd.
• Original Assignee: China MTO Limited, Daqing Petrochemical Engineering Co., Ltd.
• Inventors: Zhang, Huiling, Cheng, Longwu, Song, Zhiyuan, Min, Xiaojian
• Primary Examiner(s): Bullock, In Suk
• Assistant Examiner(s): Etherton, Bradley
• Application Number:
  US12/294,062
• Publication Number:
  US 20100234659A1
• Time in Patent Office: 2,629 Days
• Field of Search: 585/638, 585/639, 585/640, 585/802, 585/809, 585/833, 585/853, 585/854, 585/864, 585/867, 62/17, 626/25, 626/38, 629/38
• US Class Current: 585/809
• CPC Class Codes: C07C 1/20 starting from organic compounds containing only oxygen atoms as heteroatoms
• CPC Class Codes: C07C 11/04 Ethylene
• CPC Class Codes: C07C 11/06 Propene
• CPC Class Codes: C07C 7/11 by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
• CPC Class Codes: Y02P 30/20 using bio-feedstock
• CPC Class Codes: Y02P 30/40 Ethylene production

Abstract

The present invention provides a method for preparing the polymer grade low-carbon olefin through separation of the methanol pyrolysis gas, including steps of the compression, impurity removal, and absorption and separation. In the absorption and separation step, the pyrolysis gas is sent to the front-end ethylene removing column, and then is, with the C4 absorbent, further absorbed and separated to produce polymer grade ethylene products, polymer grade propylene products, and C4 and C5 products. The moderate-temperature and moderate-pressure separation without a cold box according to the present invention provides safer production process, less investment in the equipment, as well as easier separation and lower energy consumption as a result of the front-end ethylene removing and C4 absorption and separation process.

Claims

1. A method for preparing low-carbon olefin products comprising a polymer grade ethylene and/or a polymer grade propylene comprising:

(1) providing a stream of methanol pyrolysis gas comprising ethylene, propylene, C₄ hydrocarbons, and C₅ hydrocarbons, wherein the ratio of said ethylene to said propylene in said methanol pyrolysis gas is at least about 0.8 to about 1.5 by volume;

(2) compressing the methanol pyrolysis gas from step (1) in a compression system for a three- to four-stage compression, to obtain a compressed methanol pyrolysis gas having a pressure of about 1.1 to about 2.5 MPaG;

(3) removing at least one impurity from the compressed methanol pyrolysis gas from step (2) in an impurity removal system to obtain a refined methanol pyrolysis gas comprising a CO₂ concentration of less than 1 ppm and/or a total content of an alkyne less than about 5 ppm by volume;

(4) cooling said refined methanol pyrolysis gas from step (3) with a propylene refrigerant in a pyrolysis gas cooler to obtain a cooled refined methanol pyrolysis gas;

(5) passing the cooled refined methanol pyrolysis gas from step (4) into a front-end ethylene removing column comprising an upper portion and a lower portion, wherein said upper portion is maintained at a temperature ranging between about −

53°

C. and about −

26°

C., to produce an upper stream comprising ethylene and light components;

(6) passing the upper stream from the front-end ethylene removing column from step (5) to an ethylene absorption column maintained at a temperature ranging between about −

15°

C. to about −

53°

C. where an absorbent comprising C₄ hydrocarbons contacts the upper stream from the front-end ethylene removing column to produce a lower liquid stream comprised of ethylene and absorbent and an upper vapor stream comprised of absorbent, ethylene and light gases;

(7) passing the upper vapor stream from the ethylene absorption column from step (6) into an ethylene recovery column maintained at a temperature ranging between about −

68°

C. and −

34°

C. where the absorbent comprising C₄ hydrocarbons contacts the upper vapor stream from the ethylene absorption column to produce an upper stream comprised of absorbent and light gases and a lower stream comprised of ethylene and absorbent;

(8) passing the lower liquid stream from the ethylene recovery column from step (7) to the front-end ethylene removing column;

(9) passing the lower liquid stream from the ethylene absorption column from step (7) to a demethanizing column maintained at a temperature ranging between about −

27°

C. to about −

65°

C. to produce an upper stream and a lower stream;

(10) passing the lower stream from the demethanizing column in step (9) into an ethylene fractionating column maintained at a temperature ranging from about −

18°

C. to about 128°

C.; and

,

(11) obtaining polymer grade ethylene comprising greater than 99.95% by volume ethylene from the ethylene fractionating column.

2. The method of claim 1, wherein the impurity removal system used in said step (3) is selected from the group consisting of an alkaline scrubbing column, an acetylene remover, a deaerator, and a drying column and a combination thereof.

3. The method of claim 1 wherein said demethanization of said cooled refined methanol pyrolysis gas comprises removal of methane gases, said methane gases are subjected to an energy recovery through a methane gas heater followed by a passage into a PSA hydrogen generation system.

4. The method of claim 1 wherein the demethanized refined methanol pyrolysis gas is pumped into the front-end ethylene removing column, and after being mixed with the methanol pyrolysis gas, enters the front-end ethylene removing column.

11. The method of claim 1 wherein said separation of said polymer grade ethylene products occurs without the use of a cold box.

12. The method of claim 1 wherein pressure in said front-end ethylene removing column is about 0.97 MPaG.

13. The method of claim 1 wherein pressure in said ethylene absorption column is about 0.89 MPaG.

14. The method of claim 1 wherein pressure of ethylene recovery column is about 0.75 MPaG.

15. The method of claim 1 wherein pressure in said ethylene fractionating column is about 2.56 MPaG.

16. The method of claim 1 wherein each of said ethylene absorption column and said ethylene fractionating column each comprise a lower and an upper portion.

5. The method of 1 wherein said front-end ethylene removing column further comprises a lower portion maintained at a temperature ranging between about 34°

C. and about 70°

C.

6. The method of claim 5, where the components comprising propylene, C₄ hydrocarbons, and C₅ hydrocarbons are withdrawn from the lower portion of the front-end ethylene removing column and are routed to a deethanizing column from the lower portion of which the components are routed to a depropanizing column comprising an upper and a lower portion and components in the upper portion of the depropanizing column are routed through a propylene rectification tower comprising an upper and a lower portion and are further separated to obtain the polymer grade propylene comprising a volume content of propylene greater than 99.5%.

7. The method of claim 6, wherein the components in the lower portion of the depropanizing column are routed to a debutanizing column comprising an upper and a lower portion from the lower portion of which the C₅ hydrocarbons are produced.

8. The method of claim 7, wherein after the components in the lower portion of the depropanizing column enter the debutanizing column, the C₄ hydrocarbons produced in the upper portion of the debutanizing column are cooled and sent into the ethylene absorption column as the absorbent.

9. The method of claim 6, wherein after the components in the lower portion of the front-end ethylene removing column enter the deethanizing column, the materials in the upper portion of the deethanizing column are recovered and cooled to obtain the ethane products.

10. The method of claim 6, where in said lower portion of the propylene rectification tower propylene byproducts are separated.