CN108034449A - Light petrol C 5/C 6 olefin overlaps catalytic process - Google Patents
Light petrol C 5/C 6 olefin overlaps catalytic process Download PDFInfo
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- CN108034449A CN108034449A CN201810074798.2A CN201810074798A CN108034449A CN 108034449 A CN108034449 A CN 108034449A CN 201810074798 A CN201810074798 A CN 201810074798A CN 108034449 A CN108034449 A CN 108034449A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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Abstract
The light petrol C 5/C 6 olefin overlapping catalytic process that the present patent application provides, strong acid type cationic resin catalyst filling is in fixed bed reactors, light petrol containing C 5/C 6 olefin is entered by fixed bed reactors top, reaction product is exported from fixed bed reactors lower part, and the reaction pressure in fixed bed reactors is 1.0~1.5MPa, 0.5~2h of air speed‑1, reaction temperature be 60 DEG C~90 DEG C；The strong acid type cationic resin catalyst, by styrene and divinylbenzene monomers, in pore-foaming agent and the Action of Surfactant low suspension copolymerization including triethanolamine soap, sulfated castor oil, sldium lauryl sulfate and sodium glycocholate and copolymer Archon, obtained by hole purification and sulfonation.The catalyst of the technical program has embodied high-efficiency activated and stability in the C 5/C 6 olefin overlapping catalytic process of light petrol.
Description
Technical field
Present patent application is related to alkene oligomerization process in light petrol, more particularly to the Olefinic catalytic cracking of light petrol is folded
Close process.
Background technology
The issue of in September, 2017 of combination with standard administration committee of National Quality Supervision Bureau General and synchronization implementation GB 18351-2017
's《Vehicle-use alcohol gasoline（E10）》With GB 22030-2017《Vehicle-use alcohol gasoline blend component oil》Two standards, same month, state
15 ministries and commissions such as the Committee of Development and Reform of family, which combine, to issue《On expanding bio-fuel alcohol production and promoting the use of the reality of vehicle-use alcohol gasoline
Apply scheme》Notice, in northeast, Deng Duo provinces and cities promote the use of ethanol petrol from determining 2017, and plan is basic to the year two thousand twenty whole nation
Realize all standing.Though alcohol fuel, MTBE and TAME etc. are oxygen containing gasoline cleaning additives, newest standards require ethanol
Other oxygenatedchemicals, therefore, light petrol after MTBE, ether must not be artificially added in gasoline（TAME）It cannot make Deng etherificate component
For gasoline blend component, light petrol C 5/C 6 olefin is faced with new application and utilizes Pinch technology problem.
The content of the invention
The goal of the invention of present patent application is that providing a kind of light petrol C 5/C 6 olefin overlaps catalytic process,
To the C 5/C 6 olefin of light petrol, particularly 2-methyl-1-butene alkene, 2- methyl-2-butenes and dissident's alkene, implement efficiently,
Prepared by safe and environment-friendly ten/carbon of carbon benzene production, explore and open up the new application of the C 5/C 6 olefin of light petrol.
The light petrol C 5/C 6 olefin overlapping catalytic process technical solution that present patent application provides, its main skill
Art content is：A kind of light petrol C 5/C 6 olefin overlaps catalytic process, strong acid type cationic resin catalyst filling in
In fixed bed reactors, the light petrol containing C 5/C 6 olefin is entered by fixed bed reactors top, and reaction product is from fixation
Bed reactor lower part exports, and the reaction pressure in fixed bed reactors is 1.0~1.5MPa, 0.5~2h of air speed-1, reaction temperature
For 60 DEG C~90 DEG C；The strong acid type cationic resin catalyst, by styrene and divinylbenzene monomers, in pore-foaming agent and
Action of Surfactant low suspension is copolymerized and copolymer Archon, is obtained by hole purification and sulfonation：
1. is copolymerized：In the stainless steel stirred tank of reflux condensate device is configured with, water and surfactant are added, heating is adjoint
Stirring, is completely dissolved and obtains water phase；
The surfactant includes triethanolamine soap, sulfated castor oil, sldium lauryl sulfate and sodium glycocholate, and water is mutually each
Component is respectively by weight：
2000-2500 parts of water
20-50 parts of triethanolamine soap
20-50 parts of sulfated castor oil
10-30 parts of sldium lauryl sulfate
10-30 parts of sodium glycocholate；
Stainless steel stirred tank kettle temperature adds the oil phase of mixing organic phase when being warming up to 60 DEG C -70 DEG C, it is 60- to make speed of agitator
120r/min, temperature rise to 80 DEG C -90 DEG C, when polymerisation 8-10 is small, obtain copolymer Archon；
The oil phase components include styrene, divinylbenzene, expanding agent and benzoyl peroxide, and the expanding agent is just
One of any in pentane and acetone, oil phase each component is respectively by weight：
500-600 parts of styrene
400-500 parts of divinylbenzene
20-50 parts of expanding agent
10-30 parts of benzoyl peroxide；
Water phase and oil phase weight part ratio：2060-2660:930-1180；
2. holes purify：The copolymer Archon being obtained by filtration is placed in 70 DEG C of -90 DEG C of deionized waters, in -0.090--0.095MPa
Pressure under decompression boil 8-10 it is small when, then deionized water wash 3 times, room temperature is dried, and obtains Archon；
3. sulfonation：The purified Archon in hole is moved into enamel stirred tank, in stirring plus oleum, control temperature in the kettle are low
In 65 DEG C, until do not had Archon just, hereafter temperature rise to 80 DEG C -90 DEG C, reaction 2-4 it is small when, then be warming up to 100 DEG C, reaction
When 2-4 is small, be finally warming up to 120 DEG C, reaction 2-4 it is small when, thereafter in stirring, temperature be less than 40 DEG C, into kettle be added dropwise go from
Sub- water is simultaneously released at the same time, so repeatedly, untill liquid shows neutral.
Preferred means in above-mentioned overall technical architecture are, after fixed bed reactors, material pipe is in series with catalysis and steams
Tower is evaporated, is followed successively by a stripping section, multiple conversion zones and a rectifying section, strong acid in the tower reactor of the catalytic distillation tower from the bottom to top
Type cation resin catalyzing agent is filled in the conversion zone of catalytic distillation tower, and fixed bed reactors lower part output pipe, which is connected to, urges
Change the conversion zone of destilling tower, tower top materail tube road is connected with reflux condenser, and the reaction condition of catalytic distillation tower is：Tower top pressure
It is 0.3~1.0 that 0.2~0.3MPa, tower top temperature, which control the reflux ratio in 65~70 DEG C, tower,.
Strong acid type cationic resin catalyst disclosed in present patent application and its light petrol C 5/C 6 olefin overlapping should
With strong acid type cationic resin catalyst therein has suitably than surface and specific pore volume, is especially applied to the light of this programme
High-efficiency activated and stability has been embodied in the C 5/C 6 olefin overlapping catalytic process of gasoline, in practice it has proved that, through fixation
Bed reactor building-up reactions, the conversion ratio of iso-amylene reach more than 75%, and the conversion ratio of dissident's alkene reaches more than 40%, then through catalysis
Destilling tower makes unreacted C_5 olefins continue building-up reactions, react generation ten alkene of carbon and light dydrocarbon light petrol in catalytic distillation
Separated in tower, part reflux, another part discharging, bottom product pipeline are sent into gasoline hydrogenation reaction to tower top material after cooling
Device, the light dydrocarbon overlapping conversion ratio of catalytic distillation tower have reached more than 90%, and the C 5/C 6 olefin for realizing light petrol is efficient
Oligomerization, makes the C 5/C 6 olefin industrial scale of light petrol have technology and economic feasibility.The technical program
C 5/C 6 olefin building-up reactions in light petrol is produced into carbon ten/carbon benzene, is hydrogenated with again as needed, wherein
Ten alkane of carbon { isodecane, 2,4- dimethyl -3- (1- Methylethyls)-pentane } can be used as gasoline components or solvent, carbon dodecane
Hydrocarbon can be used as kerosene component or applied to cosmetic industry, low taste paint, plastic polymer reaction cosolvent and supporting agent, duplicating
Diluent, ink-jettable inks solvent and organosol formula etc., application field is extensive.
The technical program light petrol C 5/C 6 olefin building-up reactions method not only has the technological merit of method simplicity,
Existing Etherification of Light FCC Gasoline process units is also fully utilized by, existing device resource is rationally make use of, avoids existing device and washed in a pan
Eliminate, the misfortune of resource loss.
Brief description of the drawings
Fig. 1 is the system apparatus arrangements figure of present patent application.
Embodiment
Present patent application is described further below by following specific embodiment, is fully managed by these embodiments
The essence of present patent application technical solution content is solved, but the present invention is not limited only to these embodiments.
The strong acid type cationic resin catalyst that following embodiment is applied by styrene and divinylbenzene monomers,
Pore-foaming agent and the copolymerization of Action of Surfactant low suspension and copolymer Archon, obtain by hole purification and sulfonation.It is following specific
The obtained strong acid type cationic resin catalyst of embodiment, is respectively：
Catalyst C-1
1. is copolymerized：
In the stainless steel stirred tank of reflux condensate device is configured with, 2000g water and surfactant are added, heating is adjoint to stir
Mix, be completely dissolved and obtain water phase；The surfactant includes 20g triethanolamines soap, 20g sulfated castor oils, 10g bays
Alcohol sodium sulphate and 10g sodium glycocholates；
Stainless steel stirred tank kettle temperature adds the oil phase of mixing organic phase when being warming up to 60 DEG C, oil phase mixed composition includes 500g benzene second
Alkene, 400g divinylbenzenes, 20g pentanes and 10g benzoyl peroxides, it is 60r/min to make speed of agitator, and temperature rises to 80
DEG C, when polymerisation 8 is small, obtain copolymer Archon；
2. holes purify：The copolymer Archon being obtained by filtration is placed in 70 DEG C of deionized waters, is depressurized under the pressure of -0.090MPa
Boil 8 it is small when, then be washed with deionized 3 times, room temperature is dried, and obtains Archon；
3. sulfonation：The purified Archon in hole is moved into enamel stirred tank, in stirring plus oleum, control temperature in the kettle are low
In 65 DEG C, until not having Archon just；Be warming up to afterwards 80 DEG C, reaction 2 it is small when, be warming up to again thereafter 100 DEG C, reaction 2 it is small when,
Finally be warming up to 120 DEG C, reaction 2 it is small when, cooling；Hereafter in stirring, temperature is less than under conditions of 40 DEG C, is added dropwise and goes into kettle
Ionized water is simultaneously released at the same time, and so repeatedly untill the liquid shows neutral released, the physical index of this catalyst is shown in Table 1.
Fresh resin catalyst C-1 400ml are taken to be fitted into the fixed bed reactors of internal diameter 50mm, long 1000mm, it is fixed
Reaction pressure in bed reactor is 1.0MPa, air speed 0.5h-1, reaction temperature is 60 DEG C, implements light petrol C 5/C 6 olefin
Synthetic reaction experiment is overlapped, to evaluate the chemical property of prepared catalyst C-1, after testing：The iso-amylene conversion ratio of light petrol
It can reach 78%, dissident's alkene conversion ratio and can reach 42%.
Catalyst C-2
1. is copolymerized：
In the stainless steel stirred tank of reflux condensate device is configured with, 2500g water and surfactant are added, heating is adjoint to stir
Mix, be completely dissolved and obtain water phase；The surfactant includes 30g triethanolamines soap, 50g sulfated castor oils, 20g bays
Alcohol sodium sulphate and 20g sodium glycocholates；
Stainless steel stirred tank kettle temperature adds the oil phase of mixing organic phase when being warming up to 70 DEG C, oil phase mixed composition includes 600g benzene second
Alkene, 500g divinylbenzenes, 50g acetone and 30g benzoyl peroxides, it is 80r/min to make speed of agitator, and temperature rises to 85 DEG C,
When polymerisation 10 is small, copolymer Archon is obtained；
2. holes purify：The copolymer Archon being obtained by filtration is placed in 80 DEG C of deionized waters, is depressurized under the pressure of -0.095MPa
Boil 10 it is small when, then be washed with deionized 3 times, room temperature is dried, and obtains Archon；
3. sulfonation：The purified Archon in hole is moved into enamel stirred tank, in stirring plus oleum, control temperature in the kettle are low
In 65 DEG C, until not having Archon just；Be warming up to afterwards 90 DEG C, reaction 3 it is small when, be warming up to again thereafter 100 DEG C, reaction 4 it is small when,
Finally be warming up to 120 DEG C, reaction 2 it is small when, cooling；Hereafter in stirring, temperature is less than under conditions of 40 DEG C, is added dropwise and goes into kettle
Ionized water is simultaneously released at the same time, and so repeatedly untill the liquid shows neutral released, the physical index of this catalyst is shown in Table 1.
Fresh resin catalyst C-2 400ml are taken to be fitted into the fixed bed reactors of internal diameter 50mm, long 1000mm, it is fixed
Reaction pressure in bed reactor is 1.2MPa, air speed 1.5h-1, reaction temperature is 70 DEG C, implements light petrol C 5/C 6 olefin
Synthetic reaction experiment is overlapped, to evaluate the chemical property of prepared catalyst C-2, after testing：The iso-amylene conversion ratio of light petrol
It can reach 80%, dissident's alkene conversion ratio and can reach 43%.
Catalyst C-3
1. is copolymerized：
In the stainless steel stirred tank of reflux condensate device is configured with, 2200g water and surfactant are added, heating is adjoint to stir
Mix, be completely dissolved and obtain water phase；The surfactant includes 40g triethanolamines soap, 40g sulfated castor oils, 20g bays
Alcohol sodium sulphate and 20g sodium glycocholates；
Stainless steel stirred tank kettle temperature adds the oil phase of mixing organic phase when being warming up to 70 DEG C, oil phase mixed composition includes 550g benzene second
Alkene, 450g divinylbenzenes, 20g pentanes and 20g benzoyl peroxides, it is 100r/min to make speed of agitator, and temperature rises to 90
DEG C, when polymerisation 8 is small, obtain copolymer Archon；
2. holes purify：The copolymer Archon being obtained by filtration is placed in 80 DEG C of deionized waters, is depressurized under the pressure of -0.090MPa
Boil 8 it is small when, then be washed with deionized 3 times, room temperature is dried, and obtains Archon；
3. sulfonation：The purified Archon in hole is moved into enamel stirred tank, in stirring plus oleum, control temperature in the kettle are low
In 65 DEG C, until not having Archon just；Be warming up to afterwards 90 DEG C, reaction 3 it is small when, be warming up to again thereafter 100 DEG C, reaction 2 it is small when,
Finally be warming up to 120 DEG C, reaction 4 it is small when, cooling；Hereafter in stirring, temperature is less than under conditions of 40 DEG C, is added dropwise and goes into kettle
Ionized water is simultaneously released at the same time, and so repeatedly untill the liquid shows neutral released, the physical index of this catalyst is shown in Table 1.
Fresh resin catalyst C-2 400ml are taken to be fitted into the fixed bed reactors of internal diameter 50mm, long 1000mm, it is fixed
Reaction pressure in bed reactor is 1.5MPa, air speed 1.0h-1, reaction temperature is 80 DEG C, implements light petrol C 5/C 6 olefin
Synthetic reaction experiment is overlapped, to evaluate the chemical property of prepared catalyst C-3, after testing：The iso-amylene conversion ratio of light petrol
It can reach 77%, dissident's alkene conversion ratio and can reach 41%.
Catalyst C-4
1. it is copolymerized：
In the stainless steel stirred tank of reflux condensate device is configured with, 2500g water and surfactant are added, heating is adjoint to stir
Mix, be completely dissolved and obtain water phase；The surfactant includes 50g triethanolamines soap, 50g sulfated castor oils, 10g bays
Alcohol sodium sulphate and 10g sodium glycocholates；
Stainless steel stirred tank kettle temperature adds the oil phase of mixing organic phase when being warming up to 70 DEG C, oil phase mixed composition includes 550g benzene second
Alkene, 400g divinylbenzenes, 20g acetone and 20g benzoyl peroxides, it is 120r/min to make speed of agitator, and temperature rises to 80 DEG C,
When polymerisation 9 is small, copolymer Archon is obtained；
2. holes purify：The copolymer Archon being obtained by filtration is placed in 70 DEG C of deionized waters, is depressurized under the pressure of -0.095MPa
Boil 8 it is small when, then be washed with deionized 3 times, room temperature is dried, and obtains Archon；
3. sulfonation：The purified Archon in hole is moved into enamel stirred tank, in stirring plus oleum, control temperature in the kettle are low
In 65 DEG C, until not having Archon just；Be warming up to afterwards 90 DEG C, reaction 2 it is small when, be warming up to again thereafter 100 DEG C, reaction 2 it is small when,
Finally be warming up to 120 DEG C, reaction 3 it is small when, cooling；Hereafter in stirring, temperature is less than under conditions of 40 DEG C, is added dropwise and goes into kettle
Ionized water is simultaneously released at the same time, and so repeatedly untill the liquid shows neutral released, the physical index of this catalyst is shown in Table 1.
Fresh resin catalyst C-4 400ml are taken to be fitted into the fixed bed reactors of internal diameter 50mm, long 1000mm, it is fixed
Reaction pressure in bed reactor is 1.0MPa, air speed 2.0h-1, reaction temperature is 90 DEG C, implements light petrol C 5/C 6 olefin
Synthetic reaction experiment is overlapped, to evaluate the chemical property of prepared catalyst C-4, after testing：The iso-amylene conversion ratio of light petrol
It can reach 82%, dissident's alkene conversion ratio and can reach 43%.
Catalyst C-5
1. is copolymerized：
In the stainless steel stirred tank of reflux condensate device is configured with, 2000g water and surfactant are added, heating is adjoint to stir
Mix, be completely dissolved and obtain water phase；The surfactant includes 40g triethanolamines soap, 40g sulfated castor oils, 30g bays
Alcohol sodium sulphate and 20g sodium glycocholates；
Stainless steel stirred tank kettle temperature adds the oil phase of mixing organic phase when being warming up to 65 DEG C, oil phase mixed composition includes 600g benzene second
Alkene, 400g divinylbenzenes, 30g acetone and 20g benzoyl peroxides, it is 80r/min to make speed of agitator, and temperature rises to 90 DEG C,
When polymerisation 10 is small, copolymer Archon is obtained；
2. holes purify：The copolymer Archon being obtained by filtration is placed in 80 DEG C of deionized waters, is depressurized under the pressure of -0.095MPa
Boil 8 it is small when, then be washed with deionized 3 times, room temperature is dried, and obtains Archon；
3. sulfonation：The purified Archon in hole is moved into enamel stirred tank, in stirring plus oleum, control temperature in the kettle are low
In 65 DEG C, until not having Archon just；Be warming up to afterwards 90 DEG C, reaction 2 it is small when, be warming up to again thereafter 100 DEG C, reaction 3 it is small when,
Finally be warming up to 120 DEG C, reaction 4 it is small when, cooling；Hereafter in stirring, temperature is less than under conditions of 40 DEG C, is added dropwise and goes into kettle
Ionized water is simultaneously released at the same time, and so repeatedly untill the liquid shows neutral released, the physical index of this catalyst is shown in Table 1.
Fresh resin catalyst C-5 400ml are taken to be fitted into the fixed bed reactors of internal diameter 50mm, long 1000mm, it is fixed
Reaction pressure in bed reactor is 1.0MPa, air speed 1.0h-1, reaction temperature is 60 DEG C, implements light petrol C 5/C 6 olefin
Synthetic reaction experiment is overlapped, to evaluate the chemical property of prepared catalyst C-5, after testing：The iso-amylene conversion ratio of light petrol
It can reach 78.26%, dissident's alkene conversion ratio and can reach 42%.
Catalyst C-6
1. is copolymerized：
In the stainless steel stirred tank of reflux condensate device is configured with, 2300g water and surfactant are added, heating is adjoint to stir
Mix, be completely dissolved and obtain water phase；The surfactant includes 30g triethanolamines soap, 30g sulfated castor oils, 20g bays
Alcohol sodium sulphate and 10g sodium glycocholates；
Stainless steel stirred tank kettle temperature adds the oil phase of mixing organic phase when being warming up to 60 DEG C, oil phase mixed composition includes 500g benzene second
Alkene, 450g divinylbenzenes, 20g pentanes and 10g benzoyl peroxides, it is 60r/min to make speed of agitator, and temperature rises to 80
DEG C, when polymerisation 8 is small, obtain copolymer Archon；
2. holes purify：The copolymer Archon being obtained by filtration is placed in 80 DEG C of deionized waters, is depressurized under the pressure of -0.090MPa
Boil 8 it is small when, then be washed with deionized 3 times, room temperature is dried, and obtains Archon；
3. sulfonation：The purified Archon in hole is moved into enamel stirred tank, in stirring plus oleum, control temperature in the kettle are low
In 65 DEG C, until not having Archon just；Be warming up to afterwards 80 DEG C, reaction 2 it is small when, be warming up to again thereafter 100 DEG C, reaction 4 it is small when,
Finally be warming up to 120 DEG C, reaction 2 it is small when, cooling；Hereafter in stirring, temperature is less than under conditions of 40 DEG C, is added dropwise and goes into kettle
Ionized water is simultaneously released at the same time, and so repeatedly untill the liquid shows neutral released, the physical index of this catalyst is shown in Table 1.
Fresh resin catalyst C-6 400ml are taken to be fitted into the fixed bed reactors of internal diameter 50mm, long 1000mm, it is fixed
Reaction pressure in bed reactor is 1.5MPa, air speed 0.5h-1, reaction temperature is 80 DEG C, implements light petrol C 5/C 6 olefin
Synthetic reaction experiment is overlapped, to evaluate the chemical property of prepared catalyst C-6, after testing：The iso-amylene conversion ratio of light petrol
It can reach 77%, dissident's alkene conversion ratio and can reach 43%.
Catalyst C-7
1. is copolymerized：
In the stainless steel stirred tank of reflux condensate device is configured with, 2400g water and surfactant are added, heating is adjoint to stir
Mix, be completely dissolved and obtain water phase；The surfactant includes 20g triethanolamines soap, 20g sulfated castor oils, 20g bays
Alcohol sodium sulphate and 10g sodium glycocholates；
Stainless steel stirred tank kettle temperature adds the oil phase of mixing organic phase when being warming up to 70 DEG C, oil phase mixed composition includes 550g benzene second
Alkene, 450g divinylbenzenes, 20g acetone and 20g benzoyl peroxides, it is 120r/min to make speed of agitator, and temperature rises to 80 DEG C,
When polymerisation 8 is small, copolymer Archon is obtained；
2. holes purify：The copolymer Archon being obtained by filtration is placed in 80 DEG C of deionized waters, is depressurized under the pressure of -0.095MPa
Boil 8 it is small when, then be washed with deionized 3 times, room temperature is dried, and obtains Archon；
3. sulfonation：The purified Archon in hole is moved into enamel stirred tank, in stirring plus oleum, control temperature in the kettle are low
In 65 DEG C, until not having Archon just；Be warming up to afterwards 80 DEG C, reaction 4 it is small when, be warming up to again thereafter 100 DEG C, reaction 2 it is small when,
Finally be warming up to 120 DEG C, reaction 4 it is small when, cooling；Hereafter in stirring, temperature is less than under conditions of 40 DEG C, is added dropwise and goes into kettle
Ionized water is simultaneously released at the same time, and so repeatedly untill the liquid shows neutral released, the physical index of this catalyst is shown in Table 1.
Fresh resin catalyst C-7 400ml are taken to be fitted into the fixed bed reactors of internal diameter 50mm, long 1000mm, it is fixed
Reaction pressure in bed reactor is 1.5MPa, air speed 1.0h-1, reaction temperature is 80 DEG C, implements light petrol C 5/C 6 olefin
Synthetic reaction experiment is overlapped, to evaluate the chemical property of prepared catalyst C-7, after testing：The iso-amylene conversion ratio of light petrol
It can reach 79%, dissident's alkene conversion ratio and can reach 43%.
1 catalyst physical index of table
| Numbering | Catalyst | Average pore radius（nm） | Specific surface area（m2/g） | Specific pore volume ml/g |
| 1 | C-1 | 30.1 | 92.1 | 0.45 |
| 2 | C-2 | 29.3 | 82.2 | 0.45 |
| 3 | C-3 | 27.1 | 85.6 | 0.49 |
| 4 | C-4 | 29.8 | 84.9 | 0.50 |
| 5 | C-5 | 29.9 | 88.1 | 0.51 |
| 6 | C-6 | 28.5 | 78.4 | 0.50 |
| 7 | C-7 | 28.7 | 85.9 | 0.49 |
Light petrol is stored in head tank 1, and light petrol is measured the catalyst for being pumped into modularization filling or bale packing formula by metering pump 2
Fixed bed reactors 3 in building-up reactions, 3 pre-reaction product of fixed bed reactors enters back into the catalytic distillation of rear portion placed in series
The reaction was continued in tower 4, is followed successively by a stripping section, multiple conversion zones and a rectifying section in the tower reactor of catalytic distillation tower 4 from the bottom to top,
Catalyst is filled in the conversion zone of catalytic distillation tower 4 with modular or bale packing formula, and 3 lower part output pipe of fixed bed reactors connects
The conversion zone of catalytic distillation tower 4 is connected to, tower top materail tube road is connected with reflux condenser 5, and the reflux ratio of tower is 0.3~1.0.
Following light petrol C 5/C 6 olefin overlapping catalytic process embodiment concrete application is above-mentioned catalysis
The measured result of agent C-5 is, it is necessary to explanation, through testing and surveying, above others catalyst, in the pre- of fixed bed reactors
In reaction process, overlapping C_5 olefins conversion ratio reaches more than 75%, and the conversion ratio of dissident's alkene reaches more than 40%, catalytic distillation tower
Light dydrocarbon overlapping conversion ratio reached more than 90%.
Following embodiment, fixed bed reactor catalyst charge weight C-5 are 40ml, catalyst C-5 in catalytic distillation tower
Charge weight is 100ml.
The reaction condition and measured result of embodiment 1-4 is shown in Table 2：
Table 2
The reaction condition and measured result of embodiment 5-8 is shown in Table 3：
Claims (2)
1. a kind of light petrol C 5/C 6 olefin overlaps catalytic process, strong acid type cationic resin catalyst filling is in solid
In fixed bed reactor, the light petrol containing C 5/C 6 olefin is entered by fixed bed reactors top, and reaction product is from fixed bed
Reactor lower part exports, it is characterised in that reaction pressure in fixed bed reactors is 1.0~1.5MPa, 0.5~2h-1 of air speed,
Reaction temperature is 60 DEG C~90 DEG C；The strong acid type cationic resin catalyst, by styrene and divinylbenzene monomers,
Pore-foaming agent and the copolymerization of Action of Surfactant low suspension and copolymer Archon, obtain by hole purification and sulfonation：
1. is copolymerized：In the stainless steel stirred tank of reflux condensate device is configured with, water and surfactant are added, heating is adjoint
Stirring, is completely dissolved and obtains water phase；
The surfactant includes triethanolamine soap, sulfated castor oil, sldium lauryl sulfate and sodium glycocholate, and water is mutually each
Component is respectively by weight：
2000-2500 parts of water
20-50 parts of triethanolamine soap
20-50 parts of sulfated castor oil
10-30 parts of sldium lauryl sulfate
10-30 parts of sodium glycocholate；
Stainless steel stirred tank kettle temperature adds the oil phase of mixing organic phase when being warming up to 60 DEG C -70 DEG C, it is 60- to make speed of agitator
120r/min, temperature rise to 80 DEG C -90 DEG C, when polymerisation 8-10 is small, obtain copolymer Archon；
The oil phase components include styrene, divinylbenzene, expanding agent and benzoyl peroxide, and the expanding agent is just
One of any in pentane and acetone, oil phase each component is respectively by weight：
500-600 parts of styrene
400-500 parts of divinylbenzene
20-50 parts of expanding agent
10-30 parts of benzoyl peroxide；
Water phase and oil phase weight part ratio：2060-2660:930-1180；
2. holes purify：The copolymer Archon being obtained by filtration is placed in 70 DEG C of -90 DEG C of deionized waters, in -0.090--0.095MPa
Pressure under decompression boil 8-10 it is small when, then deionized water wash 3 times, room temperature is dried, and obtains Archon；
3. sulfonation：The purified Archon in hole is moved into enamel stirred tank, in stirring plus oleum, control temperature in the kettle are low
In 65 DEG C, until do not had Archon just, hereafter temperature rise to 80 DEG C -90 DEG C, reaction 2-4 it is small when, then be warming up to 100 DEG C, reaction
When 2-4 is small, be finally warming up to 120 DEG C, reaction 2-4 it is small when, thereafter in stirring, temperature be less than 40 DEG C, into kettle be added dropwise go from
Sub- water is simultaneously released at the same time, so repeatedly, untill liquid shows neutral.
2. light petrol C 5/C 6 olefin according to claim 1 overlaps catalytic process, it is characterised in that fixed bed
After reactor, material pipe be in series with catalytic distillation tower, be followed successively by one from the bottom to top in the tower reactor of the catalytic distillation tower
Stripping section, multiple conversion zones and a rectifying section, strong acid type cationic resin catalyst filling in the conversion zone of catalytic distillation tower,
Fixed bed reactors lower part output pipe is connected to the conversion zone of catalytic distillation tower, and tower top materail tube road is connected with reflux condensation mode
Device, the reaction condition of catalytic distillation tower are：0.2~0.3MPa of tower top pressure, tower top temperature control are in 65~70 DEG C, the reflux of tower
Than for 0.3~1.0.
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| CN116063152A (en) * | 2023-03-01 | 2023-05-05 | 山东京博石油化工有限公司 | Method for preparing alcohol from light gasoline |
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