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Method for preparing polymer grade 1-butene by high sulfur content four carbon compounds catalysis from refinery

A catalytic carbon, polymerization-grade technology, applied in organic chemistry, distillation purification/separation, chemical change purification/separation, etc., can solve the problems affecting the production of polymer-grade 1-butene, reducing catalyst activity, and difficult to control product quality, etc. To achieve the effect of low cost, quality control and production safety

Active Publication Date: 2011-09-07
CHINA PETROLEUM & CHEM CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The sulfur-containing mixed C4 in the catalytic cracking unit of the refinery not only contains isobutane, 1-butene, isobutene, cis-2-butene, trans-2-butene, n-butane and a small amount of dienes, but also contains methane Mercaptan, ethanethiol, propanethiol, isopropylthiol, butanethiol, n-pentanethiol, methyl sulfide, methyl ethyl sulfide, carbonyl sulfide, dimethyl disulfide, methyl ethyl disulfide, di Trace inactive sulfides such as ethylene disulfide and thiophene (see Table 1 for details), the total sulfur is about 100-2500 mg / m 3 , these sulfides will significantly reduce the activity of the catalyst after being adsorbed on the catalyst during processing, thereby seriously affecting the production of polymerization-grade 1-butene; After the removal of isobutene, the remaining C4 undergoes selective hydrodediene and distillation separation to produce polymer-grade 1-butene while removing sulfides. This process is not suitable for high-sulfur mixed C4 materials, It is difficult to control product quality in industrial production and the production process is prone to catalyst poisoning

Method used

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  • Method for preparing polymer grade 1-butene by high sulfur content four carbon compounds catalysis from refinery
  • Method for preparing polymer grade 1-butene by high sulfur content four carbon compounds catalysis from refinery
  • Method for preparing polymer grade 1-butene by high sulfur content four carbon compounds catalysis from refinery

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Embodiment 1

[0028] By-products of catalytic cracking units in refineries contain at least isobutane, 1-butene, isobutene, cis-2-butene, trans-2-butene, n-butane and a small amount of dienes, carbon five fractions, and high-sulfur compounds (Total sulfur is about 100~2500mg / m 3 , including mercaptans, sulfides, carbonyl sulfide, disulfides, thiophenes) and other components of mixed carbon four as raw materials, into the deC 5 Tower, the diameter of the tower is φ2200mm, it is a tray tower, the feeding position is on the 15th plate theoretical plate from top to bottom, the reflux ratio is 3, the top pressure is 0.4MPa (absolute), and the top temperature is 43°C. The weight ratio of the top of the tower to the bottom material is 10:1, and part of the isobutane, 1-butene, isobutene, 2-butene, dienes, and low sulfur compounds in the raw material are separated from the top of the tower, and the total sulfur is about 30~150mg / m 3 , to achieve the purpose of desulfurization of mixed carbon four...

Embodiment 2

[0044] With the mixed carbon four of embodiment 1 as raw material, enter de-C 5 Tower, the diameter of the tower is φ2200mm, it is a tray tower, the feeding position is the 20th theoretical plate from top to bottom, the reflux ratio is 80, the top pressure is 0.8MPa (absolute), the top temperature is 28°C, The weight ratio of tower top and bottom materials is 5:1; the operating conditions for primary desulfurization are pressure 0.3MPa (absolute), temperature 70°C, oil agent weight ratio 10:1, oil agent contacts in the same direction, and agent liquid circulation Use; drying and organic sulfur removal operating conditions are: pressure 0.3MPa (absolute), temperature 70 ℃, liquid space velocity 5h -1 , the filling height of the drying tower is 5.5m, and the filling height of the desulfurization agent is 7m; Direct contact, agent liquid recycling; water washing operating conditions: pressure 0.3MPa (absolute), temperature 70 ° C, oil-water weight ratio 15:1, oil-water contact i...

Embodiment 3

[0046] With the mixed carbon four of embodiment 1 as raw material, and the decarburization of the same condition 5 Tower, the pressure is 1.2MPa (absolute), the temperature at the top of the tower is 95°C, the reflux ratio is 150, the weight ratio of the top of the tower and the bottom material is 1:1, the operating conditions for the first-stage desulfurization are pressure 0.3MPa (absolute), and the temperature is 70°C, the weight ratio of the oil agent is 10:1, the oil agent is in contact with the same direction, and the agent liquid is recycled; the operating conditions for drying and removing organic sulfur are: pressure 2.2MPa (absolute), temperature 100°C, liquid space velocity 10h -1, the filling height of the drying tower is 5m, and the filling height of the desulfurization agent is 7m; the operating conditions of the secondary desulfurization process are pressure 2.2MPa (absolute), temperature 100°C, oil agent weight ratio 1:1, and oil agents contacting in the same di...

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Abstract

The invention relates to a method for producing polymer grade 1-butene from C4 catalyzed by high sulfur in a refinery, which is a purification method for C4 catalyzed by the high sulfur that is the by-product of refinery process in petrochemical industry. The invention discloses that coarse desulfurization of the C4 catalyzed by a high sulfur refinery is carried out in a de-C5 tower, and at least desulfurizing, drying, organic sulfur removing and washing are carried out by a water scrubber and a reactor, thereafter, material flow enters the reactor and etherification is carried out for removing isobutene, as well as hydrogenation is added selectively and removing diene. Then the material flow is separated by a distillation column, and adsorbed by a molecular sieve in the reactor, so as to obtain the polymer grade 1-butene with the purity of the 1-butene to be over 99 percent, wherein, the total sulfur content is less than 2mg / m<3>. By adopting the invention, the mixed C4 with high sulfur is desulfurized at first until the sulfur content is less than 10mg / m<3>, and then enters different reactors, and the catalyst activity is not affected, thus leading the 1-butene to achieve polymer grade standard finally. The production technique of the invention is characterized by short process, easy operation, and the like, and has the advantages of environmental sanitation, safe production and comparatively low cost.

Description

technical field [0001] The present invention relates to a kind of method for preparing polymer grade 1-butene, more specifically, the present invention relates to a kind of method of utilizing the high-sulfur mixed carbon four produced by refinery catalytic cracking unit to prepare polymer grade 1-butene method. Background technique [0002] Polymerization grade 1-butene is used as a comonomer of polyethylene to produce high-density polyethylene and linear low-density polyethylene. Polymerization grade 1-butene requires high-purity 1-butene, and has high requirements for other impurities, such as 1-butene content greater than 99% (m / m), sulfur content less than 2mg / m 3 , The diene content is less than 200mg / kg. With the improvement of my country's crude oil processing capacity, the catalytic cracking unit of the refinery will produce a large amount of mixed C4 by-products, and the production of polymer grade 1-butene from a large amount of surplus and cheap mixed C4 is a c...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C11/08C07C7/148C07C7/04
Inventor 姜立良唐旭东杨栋付建周永生程佩双李连福
Owner CHINA PETROLEUM & CHEM CORP
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