CN110054543A - Using sulfur dioxide as the method for the C4 component hydrogenation and removing butadiene of regulator - Google Patents

Using sulfur dioxide as the method for the C4 component hydrogenation and removing butadiene of regulator Download PDF

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CN110054543A
CN110054543A CN201910408523.2A CN201910408523A CN110054543A CN 110054543 A CN110054543 A CN 110054543A CN 201910408523 A CN201910408523 A CN 201910408523A CN 110054543 A CN110054543 A CN 110054543A
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regulator
sulfur dioxide
stage hydrogenation
hydrogenation reactor
support carrier
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CN110054543B (en
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刘超
侯鹏
赵艳东
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DALIAN HUABANG CHEMICAL Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C07C5/05—Partial hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The present invention discloses a kind of using sulfur dioxide as the method for the C4 component hydrogenation and removing butadiene of regulator, and the loaded catalyst of one-stage hydrogenation reactor and second-stage hydrogenation reactor is 3m3, the catalyst is by active component, selective auxiliary agent and carrier is supported to form, active component Pd, and selective auxiliary agent is Co, Ru and Ag, and support carrier is γ Al2O3、CeO2‑ZrO2And the mixture of attapulgite；H2Alkadienes molar ratio in total input and raw material is 2~4, the 50~90% of the total input of hydrogen input Zhan of one-stage hydrogenation reactor, the 10~50% of the total input of hydrogen input Zhan of second-stage hydrogenation reactor；Hydrogenation reaction pressure is 2.0Mpa, after reacting balance, is passed through the regulator 5h that flow is 1Nm/h to the road Jia Qingzong, the regulator is sulfur dioxide and N2Gaseous mixture, the volumetric concentration of sulfur dioxide is 0.05%~5% in regulator, surplus N2。

Description

Using sulfur dioxide as the method for the C4 component hydrogenation and removing butadiene of regulator
Technical field
The present invention relates to a kind of method of four component selection hydrogenation and removing butadiene of carbon, especially one kind takes into account butadiene Depth is removed with 1- butylene yield using sulfur dioxide as the method for the C4 component hydrogenation and removing butadiene of regulator.
Background technique
Four component of carbon is the general name of alkane, monoolefine and alkadienes, is mainly derived from petroleum olefin cracking, coal chemical industry MTO Device product.Petroleum olefin cracking device is to produce based on ethylene, while four component of propylene simultaneously and carbon, and carbon four mainly produces MTBE and only son's alkene；Coal chemical industry MTO device prepares alkene, ethylene and propylene, while generating four product of part carbon, and carbon four is used for Produce the products such as MTBE, 1- butylene and 2PH.Since four component of carbon contains alkadienes, it is easy polymerization blocking production under certain condition The catalyst duct of MTBE, 1- butylene and 2PH integration unit, it is therefore necessary to be removed before following process.It generally adopts at present Removal methods are selective hydrogenations.Selective hydrogenation is that four component of carbon reacts with hydrogen under the effect of the catalyst, In addition to the main reactions such as removing alkadienes, it is accompanied by side reaction, such as the isomerization reaction of alkadienes, 1- butylene adds hydrogen saturated reaction And isobutene adds hydrogen saturated reaction etc., side reaction can cause valuable component (1- butylene etc.) loss in raw material.
Existing four component selection hydrogenation plant of carbon has two sections of selective hydrogenations, adds with one-stage hydrogenation reactor, two sections Hydrogen reactor, surge tank, preheater, flow control valve and hydrogenation plant etc., hydrogenation plant is by adding hydrogen two branch of total Lu Houfen Road, and each branch is further divided into middle part branch and lower part branch, enters hydrogenation reaction from the middle part of hydrogenator, lower part respectively Device, distribute each hydrogenator by the flow valve in pipeline plus hydrogen amount.The C4 raw material of upstream be dehydrated, preheated after with lower part Enter one-stage hydrogenation reactor lower part after the hydrogen mixing on road, after Jing Yici catalytic hydrogenation reaction again with second-stage hydrogenation reactor Lower part branch hydrogen is mixed into second-stage hydrogenation reactor, condensed after quadric catalysis hydrogenation reaction, flash after export.Institute at present Active high, large specific surface area is striven with catalyst, increases side reaction while pursuing main reaction, is substantially all that there is fourths The problem of diene removing depth and 1- butylene yield cannot be taken into account, butadiene removal depth (residual volume) is greater than 1ppm, 1- butylene Yield is less than 99%.
Summary of the invention
The present invention is to provide one kind in order to solve above-mentioned technical problem present in the prior art and take into account butadiene removal depth Degree is with 1- butylene yield using sulfur dioxide as the method for the C4 component hydrogenation and removing butadiene of regulator.
The technical solution of the invention is as follows: a kind of using sulfur dioxide as the C4 component hydrogenation and removing butadiene of regulator Method, using two sections of selective hydrogenation equipment with one-stage hydrogenation reactor and second-stage hydrogenation reactor, it is characterised in that:
The loaded catalyst of one-stage hydrogenation reactor and second-stage hydrogenation reactor is 3m3, the catalyst is by active component, choosing Selecting property auxiliary agent and support carrier composition, active component Pd, selective auxiliary agent are Co, Ru and Ag, and support carrier is γ Al2O3、 CeO2-ZrO2And the mixture of attapulgite；The Pd is support carrier quality 0.08%~1.5%, the selectivity auxiliary agent Co, Ru, Ag are support carrier quality 1 ~ 1.5%, γ Al in the support carrier respectively2O3、CeO2-ZrO2, attapulgite Mass percent is respectively 50 ~ 60%, 30 ~ 40%, 10 ~ 20%；
H2Alkadienes molar ratio in total input and raw material is 2~4, the 50 of the total input of hydrogen input Zhan of one-stage hydrogenation reactor ~90%, the 10~50% of the total input of hydrogen input Zhan of second-stage hydrogenation reactor, the middle part branch of each section of hydrogenator and Lower part branch hydrogen respectively accounts for 50%；
Hydrogenation reaction pressure is 2.0Mpa, and after reacting balance, the regulator 5h for being passed through that flow is 1Nm/h to the road Jia Qingzong is described Regulator is sulfur dioxide and N2Gaseous mixture, the volumetric concentration of sulfur dioxide is 0.05%~5% in regulator, surplus N2。
The present invention is two sections of process for selective hydrogenation, uses high-selectivity hydrogenation catalyst and regulator, passes through control The concentration and additional amount of sulfur dioxide inactivate catalyst surface active component Parts, can meet butadiene hydrogenation and generate 1- fourth Alkene makes butadiene removal depth 0.97ppm, while avoiding generating excessive side reaction, and 1- butylene yield 101.23% can fit extensively For large-scale industrial production.
Specific embodiment
It is of the invention using sulfur dioxide as the method for the C4 component hydrogenation and removing butadiene of regulator, using have one section plus Two sections of selective hydrogenation equipment of hydrogen reactor and second-stage hydrogenation reactor, specific design are as follows:
The loaded catalyst of one-stage hydrogenation reactor and second-stage hydrogenation reactor is 3m3, the catalyst is by active component, choosing Selecting property auxiliary agent and support carrier composition, active component Pd, selective auxiliary agent are Co, Ru and Ag, and support carrier is γ Al2O3、 CeO2-ZrO2And the mixture of attapulgite；The Pd is support carrier quality 1.5%, described selectivity auxiliary agent Co, Ru, Ag It is support carrier quality 1%, γ Al in the support carrier respectively2O3、CeO2-ZrO2, attapulgite mass percent point It Wei 50%, 40%, 10%；
The preparation method of catalyst successively carries out in accordance with the following steps:
A. 1000gCeCl is weighed3And 1000gZrCl4, the ammonia spirit of 2L aqueous solution and mass concentration 0.35% is prepared, it is coprecipitated Shallow lake method generates CeO2-ZrO2Mixture washes CeO2-ZrO2To mixture without Cl-Until, 120 DEG C of dry 5h are made 1150gCeO2-ZrO2Mixture；
B. 400gCeO is taken2-ZrO2、500gγAl2O3And 100g attapulgite, banded extruder is used again after evenly mixing with blender Being extruded into 1/8, " 1.7-2.5mm spheric granules is made with sugar coating machine in bar shaped, and water mist health is dried afterwards for 24 hours, using N2Protective program Catalyst support carrier is made after being warming up to 450 DEG C of roastings；
C. with quantitative PdCl2、CoCI2、RuCl3、AgNO3, the concentrated hydrochloric acid of 2ml mass concentration 37%, 200ml deionized water add Mixed solution is made in heat of solution；
D. the catalyst support carrier 500g for taking above-mentioned preparation, 1h is impregnated in isometric mixed solution, uses mass concentration later 2% glucose (reducing catalyst) 500ml impregnates 1h, is washed to no Cl-Until, 120 DEG C of dry 12h after drying.
It is 7435.52kg/h, the total 4.3~8.6Kg/h of additional amount of hydrogen, one-stage hydrogenation reaction that C4, which feeds (index such as table 1), The 80% of the total input of hydrogen input Zhan of device, the 20% of the total input of hydrogen input Zhan of second-stage hydrogenation reactor, every one-stage hydrogenation is anti- The middle part branch and lower part branch hydrogen for answering device respectively account for 50%；
Hydrogenation reaction pressure is 2.0Mpa, and first time device is driven after operation, detects raw material and product alkadienes, 1- fourth with chromatography Alkene content is passed through the regulator 5h that flow is 1Nm/h to the road Jia Qingzong, the regulator is sulfur dioxide after reacting balance With N2Gaseous mixture, the volumetric concentration of sulfur dioxide is 0.1% in regulator, surplus N2。
After operation 1 month, unimplanted highly selective regulator (comparative example) and index of the embodiment of the present invention respectively such as table 2, Table 3.
Table 1
Serial number Component kg/h wt%
1 ISOC4H10 10.13 0.14
2 N-C4H10 337.88 4.54
3 T-C4H8 2399.25 32.27
4 1-C4H8 2192.25 29.48
5 ISOC4H8 337.88 4.54
6 C-C4H8 2041.13 27.45
7 Butadiene 117 1.57
It amounts to 7435.52
Table 2
Serial number Component kg/h wt%
1 ISOC4H10 10.6 0.14
2 N-C4H10 381.02 5.12
3 T-C4H8 2450.5 32.94
4 1-C4H8 2173.77 29.22
5 ISOC4H8 370.05 4.98
6 C-C4H8 2052.21 27.59
7 Butadiene 0.0071 0.000096
It amounts to 7438.16 100
Table 3
Serial number Component kg/h wt%
1 ISOC4H10 16.1 0.22
2 N-C4H10 372.09 5.00
3 T-C4H8 2420.5 32.54
4 1-C4H8 2219.2 29.84
5 ISOC4H8 356.04 4.79
6 C-C4H8 2054.22 27.62
7 Butadiene 0.0072 0.000097
It amounts to 7438.16 100
The performance comparison of the embodiment of the present invention and comparative example such as table 4.
Table 4
Project Butadiene removal depth ppm 1- butylene yield %
Comparative example 0.96 99.16
The embodiment of the present invention 0.97 101.23
By comparison as can be seen that removing depth 0.97ppm, the 1- butylene yield 101.23% of alkadienes of the embodiment of the present invention, simultaneous Butadiene removal depth and 1- butylene yield are cared for, large-scale industrial production can be met.

Claims (1)

1. it is a kind of using sulfur dioxide as the method for the C4 component hydrogenation and removing butadiene of regulator, it is reacted using with one-stage hydrogenation Two sections of selective hydrogenation equipment of device and second-stage hydrogenation reactor, it is characterised in that:
The loaded catalyst of one-stage hydrogenation reactor and second-stage hydrogenation reactor is 3m3, the catalyst is by active component, choosing Selecting property auxiliary agent and support carrier composition, active component Pd, selective auxiliary agent are Co, Ru and Ag, and support carrier is γ Al2O3、 CeO2-ZrO2And the mixture of attapulgite；The Pd is support carrier quality 0.08%~1.5%, the selectivity auxiliary agent Co, Ru, Ag are support carrier quality 1 ~ 1.5%, γ Al in the support carrier respectively2O3、CeO2-ZrO2, attapulgite Mass percent is respectively 50 ~ 60%, 30 ~ 40%, 10 ~ 20%；
H2Alkadienes molar ratio in total input and raw material is 2~4, the 50 of the total input of hydrogen input Zhan of one-stage hydrogenation reactor ~90%, the 10~50% of the total input of hydrogen input Zhan of second-stage hydrogenation reactor, the middle part branch of each section of hydrogenator and Lower part branch hydrogen respectively accounts for 50%；
Hydrogenation reaction pressure is 2.0Mpa, and after reacting balance, the regulator 5h for being passed through that flow is 1Nm/h to the road Jia Qingzong is described Regulator is sulfur dioxide and N2Gaseous mixture, the volumetric concentration of sulfur dioxide is 0.05%~5% in regulator, surplus N2。
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101500968A (en) * 2005-04-15 2009-08-05 催化蒸馏技术公司 Double bond hydroisomerization process
CN105399593A (en) * 2014-09-16 2016-03-16 中国石油化工股份有限公司 Method for preparing 1-butene through selective hydrogenation of 1,3-butadiene in C4 distillates
US20160176783A1 (en) * 2014-12-17 2016-06-23 Uop Llc Selective hydrogenation method
CN106582625A (en) * 2015-10-14 2017-04-26 中国石油化工股份有限公司 Catalyst for selective hydrogenation of butadiene
CN108014832A (en) * 2016-11-01 2018-05-11 中国石油化工股份有限公司 The hydrogenation technique of C-2-fraction in selective hydrogenation catalyst and its application and preparing ethylene by steam cracking
CN108689789A (en) * 2017-04-07 2018-10-23 中国石油化工股份有限公司 A kind of C4The method that fraction selective hydrogenation prepares 1- butylene
CN108837831A (en) * 2018-06-29 2018-11-20 万华化学集团股份有限公司 A kind of selective hydrogenation of butadiene 1- butylene catalyst and its preparation method and application
CN108863695A (en) * 2017-05-15 2018-11-23 中国石油天然气股份有限公司 A kind of hydrotreating method mixing four raw material of carbon
CN109092298A (en) * 2017-06-21 2018-12-28 中国石油化工股份有限公司 For cracking c_4 selective hydrogenation catalyst

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101500968A (en) * 2005-04-15 2009-08-05 催化蒸馏技术公司 Double bond hydroisomerization process
CN105399593A (en) * 2014-09-16 2016-03-16 中国石油化工股份有限公司 Method for preparing 1-butene through selective hydrogenation of 1,3-butadiene in C4 distillates
US20160176783A1 (en) * 2014-12-17 2016-06-23 Uop Llc Selective hydrogenation method
CN106582625A (en) * 2015-10-14 2017-04-26 中国石油化工股份有限公司 Catalyst for selective hydrogenation of butadiene
CN108014832A (en) * 2016-11-01 2018-05-11 中国石油化工股份有限公司 The hydrogenation technique of C-2-fraction in selective hydrogenation catalyst and its application and preparing ethylene by steam cracking
CN108689789A (en) * 2017-04-07 2018-10-23 中国石油化工股份有限公司 A kind of C4The method that fraction selective hydrogenation prepares 1- butylene
CN108863695A (en) * 2017-05-15 2018-11-23 中国石油天然气股份有限公司 A kind of hydrotreating method mixing four raw material of carbon
CN109092298A (en) * 2017-06-21 2018-12-28 中国石油化工股份有限公司 For cracking c_4 selective hydrogenation catalyst
CN108837831A (en) * 2018-06-29 2018-11-20 万华化学集团股份有限公司 A kind of selective hydrogenation of butadiene 1- butylene catalyst and its preparation method and application

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