CN109456179A - A kind of method that oil refinery dry gas prepares ethyl acetate - Google Patents
A kind of method that oil refinery dry gas prepares ethyl acetate Download PDFInfo
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- CN109456179A CN109456179A CN201710794699.7A CN201710794699A CN109456179A CN 109456179 A CN109456179 A CN 109456179A CN 201710794699 A CN201710794699 A CN 201710794699A CN 109456179 A CN109456179 A CN 109456179A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
Abstract
The present invention provides a kind of method that oil refinery dry gas prepares ethyl acetate, using dilute ethylene in Oil Refinery Industry device by-product dry gas as raw material, ethyl acetate is produced with the co-feeding progress esterification of vapourised acetic acid under the effect of carried heteropoly acid salt catalyst using fixed bed reactors.Reaction temperature is 150~200 DEG C, and reaction pressure is 0.5~3.0MPa, and the air speed of dry gas is 500~3000h‑1, acetic acid liquid air speed are as follows: 0.1~1.0h‑1, acetic acid and ethylene molar ratio are 1:1~10；Acetic acid and water molar ratio are 1:0.05~1.The present invention is raw material using low-concentration ethane in refinery facilities by-product dry gas, needs not move through separating-purifying, considerably reduces production cost, reduces energy consumption.The present invention also provides the preparation method of carried heteropoly acid salt catalyst, which shows higher ethyl acetate space-time yield, and significantly improves the stability of catalyst, is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of methods that oil refinery dry gas prepares ethyl acetate, are about using porous oxygen more specifically
Dilute ethylene and the highly selective system of the co-feeding progress esterification of vapourised acetic acid in SiClx carried heteropoly acid salt catalyst catalysis drying gas
Standby ethyl acetate.The invention further relates to the preparation methods of heteropolyacid salt catalyst.
Background technique
Ethyl acetate is called and does ethyl acetate, is a kind of important organic solvent and chemical industry raw material, it is a kind of nothing
Color is transparent and has the flammable liquid of mobility, volatile, there is fruit aroma.Ethyl acetate be mainly used as coating (paint and
Enamel paint) active solvent in ink and adhesive formula, it is also possible to make the process solvent of pharmacy and organic chemical synthesis.It is close
Year, it is continuous as product quantities such as high-grade solvent production adhesive, ink, coating as the industry developments such as automobile, building are rapid
Increase, further increases ethyl acetate demand, there is extraordinary development prospect.
Currently, the production method of ethyl acetate mainly has acid esterification method, acetaldehyde condensation method and alcohol dehydrogenase method.The world is each
State selects different process routes according to respective resources advantage, and the ethyl alcohol and acetic acid in the U.S. are cheap and in liberal supply, because
This its leading technology is alcohol, acetic acid direct esterification；Europe and Japan then mostly use acetaldehyde condensation method, because it has largely
Acetaldehyde resource.Alcohol dehydrogenase method is although technologically advanced and environmental-friendly, but is confined to catalyst choice and conversion ratio is not high, secondary
Product is more, and the reasons such as separation difficulty, there is presently no carry out commercialized running.And the ethyl acetate in China is then mainly using tradition
Acid esterification method produced.Catalyst needed for the technique generallys use the concentrated sulfuric acid, its advantage is that technology maturation, and can be with
Butyl acetate is prepared by switching raw materials for production, the disadvantage is that catalyst is strong to equipment corrosion, wastewater flow rate is big, maintenance cost is high
Deng.
The production technology of newest ethyl is Addition on ethylene esterification process, uses ethylene for raw material, in acidic catalyst
Lower acetic acid and ethylene direct esterification synthesizing ethyl acetate are acted on, this method belongs to atom economic reaction, almost without extra
By-product generates, and simple process is suitable for being mass produced, and shows good development prospect.Showa Denko K. K exists
US5189201 is disclosed makes the compound containing unsaturated ethylene linkage and acetic acid anti-using tungsten and molybdenum heteropolyacid i.e. salt as catalyst
The technique for answering synthesizing carboxylate；BP Chemicals Ltd is also disclosed with heteropoly acid in CN1953958A as catalysis
Agent, in the research work of fixed bed reactors synthesizing ethyl acetate.It is all to use pure ethylene for original in technology exemplified above
Material, and the production capacity wretched insufficiency of China's ethylene, China's ethylene production capacity in 2015 is 22,640,000 tons, and the consumption of ethylene equivalent is 3733
Ten thousand tons, domestic ethylene largely will also rely on import.
On the other hand, the annual by-product dry gas in oil refining enterprise, China is more than 6.0Mt/a, and wherein ethylene yield is 1.0Mt/a left
It is right.In the dilute ethylene use aspects of dry gas, there are mainly two types of approach, and one is recycling polymer grade ethylenes；Another kind is in dry gas
Dilute ethylene is directly processed, and more mature industrialization technology is preparing ethylbenzene from dry gas technology, there is successful industry both at home and abroad
Using.However, still using there are also a large amount of dry gas resource as fuel, the waste of ethylene resource is caused, therefore it is dry to develop refinery
It is to improve another effective way of dry gas comprehensive utilization that gas, which prepares ethyl acetate technology,.
Summary of the invention
The present invention provides a kind of method that oil refinery dry gas prepares ethyl acetate, is to prepare ethyl acetate based on Addition on ethylene method
Mechanism, carried heteropoly acid salt catalyst effect under, utilize dilute ethylene in Oil Refinery Industry device by-product dry gas and vaporization second
The co-feeding direct esterification of acid generates ethyl acetate.It is another object of the present invention to provide the preparation sides of above-mentioned catalyst
Method.
The purpose of the invention is achieved by the following technical solution: the preparation method of ethyl acetate is using fixed bed reaction
Device passes through the catalysis of loading silicon dioxide with heteropoly acid salt with dilute ethylene in Oil Refinery Industry device by-product dry gas and vapourised acetic acid together
Agent, direct addition esterification obtain ethyl acetate.Reaction process condition: reaction temperature be 150~200 DEG C, reaction pressure be 0.5~
3.0MPa, the air speed of dry gas are 500~5000h-1, acetic acid liquid air speed are as follows: 0.1~1.0h-1, ethylene is with acetic acid molar ratio
1:1~10, acetic acid and water molar ratio are 1:0.1~1；
Optimum process condition are as follows: reaction temperature is 160~190 DEG C, and reaction pressure is 1.5~2.5MPa, the air speed of dry gas
For 1000~3000h-1, acetic acid liquid air speed are as follows: 0.2~0.8h-1, acetic acid and ethylene molar ratio are 1:2~6；Acetic acid rubs with water
You are than being 1:0.15~0.75.
The heteropolyacid salt catalyst includes: porous silica load Keggin-type phosphotungstate, silicotungstate, phosphomolybdic acid
Salt, P-Mo-Wo acid salt one or more combination；And replace these sour hydrogen atoms counter cation be larger ionic radius not
It is dissolved in K, Rb, Cs and NH of water4Salt, wherein preferably carried phospho-tungstic acid cesium salt catalyst.
The porous oxidation silicon carrier is ordered meso-porous silicon oxide molecular sieve, amorphous silicon oxide, artificial synthesized silica gel
Or one of natural silica gel, specific surface area are as follows: 50~500m2/ g, average pore size are as follows: 6~40nm.It is wherein preferably artificial to close
At silica gel, specific surface area are as follows: 80~400m2/ g, average pore size are as follows: 8~30nm.
Catalyst preparation process of the invention carries out in the steps below:
1,3~5% dust technologies of porous silica are handled 2~10 hours, then is washed with deionized to pH=7 and is
Only, 100~120 DEG C drying 12 hours, 600~800 DEG C roast 4 hours, and pretreated silica support is made.
2, a certain amount of potassium, rubidium, caesium or ammonium salt presoma is weighed to be dissolved in suitable deionized water, what addition pre-processed
Silica, after drying in the shade naturally, 100~120 DEG C drying 2~20 hours.
3, the silica being modified is mixed with suitable heteropoly acid aqueous solution, adsorbs its saturation, it is slow in 90 DEG C of water-baths
Slow evaporating water, 100~120 DEG C drying 2~20 hours, 200~300 DEG C roast 2~10 hours.By changing counter cation
Concentration, the carried heteropoly acid salt catalyst that different counter cations replace can be prepared.
4, wherein heteropolyacid salt accounts for 10~50wt% of the carried heteropoly acid salt catalyst total weight.
5, the 0.05~3.0% of counter cation and the heteropolyacid salt molar ratio wherein is introduced by ion exchange.
The present invention has the following advantages that compared with prior art and effect: since pure ethylene cost is very high, the present invention is used
Dilute ethylene is raw material in oil plant by-product dry gas, needs not move through separating-purifying, the production cost of raw material can be greatly lowered,
Reduce energy consumption, provides a new approach for the preparation of ethyl acetate.Carried heteropoly acid salt catalyst provided by the invention,
Not only acetic acid conversion with higher and high ethyl acetate selectivity and space-time yield, but also show preferable stabilization
Property.The present invention also provides the preparation method of carried heteropoly acid salt catalyst, which shows higher ethyl acetate
Space-time yield, and the stability of catalyst is significantly improved, it is suitable for industrialized production.
Detailed description of the invention
Fig. 1 embodiment 12 and 4 catalyst of comparative example carry out the experimental result of 120 hours acetic acid conversions in reaction.
Fig. 2 embodiment 12 and 4 catalyst of comparative example carry out the experimental result of 120 hours ethyl acetate selectivity in reaction.
Specific embodiment
Dilute ethylene with acid esterification addition reaction is carried out on fixed bed reactors in dry gas.Reactor is that internal diameter is
The 316L stainless steel tube of 9mm, loaded catalyst 6ml, reaction pressure are controlled by pressure-regulating valve, acetic acid with go in right amount
Ionized water mixing is squeezed into micro high-pressure plunger pump-metered, carries out temperature control using precise temperature control instrument, temperature-controlled precision is ± 1
℃.Specific reaction condition is as follows: reaction temperature is 180 DEG C, reaction pressure 2.0MPa, and the air speed of dry gas is 1500h-1, acetic acid
Feed space velocities are 0.3h-1, acetic acid and ethylene molar ratio are 1:5, and acetic acid and water molar ratio are 1:0.2.After reaction carries out 24 hours
Sampling analysis.Using the Agilent7890 gas chromatographic analysis of assembly FFAP capillary column, gas phase after the cooling collection of liquid product
Product uses the Agilent 3000A Micro GC gas chromatographic analysis for assembling Plot Q column.Catalytic performance is listed in table 2.
Dry gas raw material (refinery's cracking gas) composition that the present invention uses is shown in Table 1, but the composition is not intended to limit refinery's cracking gas.
1 refinery's cracking gas of table composition
| Component | Content (wt%) |
| H2 | 1.73 |
| CO | 0.1 |
| CH4 | 29.98 |
| C2H4 | 58.31 |
| C2H6 | 9.77 |
| C3H4 | 0 |
| C3H6 | 0.11 |
| C3H8 | 0 |
The present invention will be further described combined with specific embodiments below, but the present invention is not intended to limit these embodiments.
Embodiment 1
(1) by artificial synthesized silica gel SiO220~40 mesh are broken for, are handled 4 hours with 3% dust technology of mass concentration, then use
Deionized water is repeatedly washed until pH=7,120 DEG C drying 12 hours, 700 DEG C roast 4 hours, obtain pretreated SiO2It carries
Body.
(2) 0.026g potassium carbonate is weighed, 20ml deionized water is added, after being uniformly dissolved, impregnates the pretreated SiO of 16.0g2
Carrier dries in the shade naturally, 120 DEG C drying 12 hours.
(3) it weighs 10.66g phosphotungstic acid to be dissolved in 40ml deionized water, SiO will be modified2Dipping wherein, it is small to stand 2
When, it is stirred continuously in 90 DEG C of water-baths and is evaporated liquid, 10 hours dry at 120 DEG C, 200 DEG C roast 10 hours, and SiO is made2It is negative
What is carried contains 40% phosphotungstic acid sylvite catalyst, i.e. 40%K0.1H2.9PW12O40/SiO2。
Embodiment 2
Using the pretreated artificial synthesized silica gel of step (1) in embodiment 1.
0.042g rubidium carbonate is weighed, 20ml deionized water is added, after being uniformly dissolved, impregnates the pretreated carrier of 16.0g, from
So dry in the shade, 120 DEG C drying 12 hours.
It weighs 10.66g phosphotungstic acid to be dissolved in 40ml deionized water, SiO will be modified2Dipping wherein, stands 2 hours,
It is stirred continuously in 90 DEG C of water-baths and is evaporated liquid, 10 hours dry at 120 DEG C, 200 DEG C roast 10 hours, and SiO is made2Load
Containing 40% phosphotungstic acid rubidium salt catalyst, i.e. 40%Rb0.1H2.9PW12O40/SiO2。
Embodiment 3
Using the pretreated artificial synthesized silica gel of step (1) in embodiment 1.
0.06g cesium carbonate is weighed, 20ml deionized water is added, after being uniformly dissolved, impregnates the pretreated carrier of 16.0g, from
So dry in the shade, 120 DEG C drying 12 hours.
It weighs 10.66g phosphotungstic acid to be dissolved in 40ml deionized water, SiO will be modified2Dipping wherein, stands 2 hours,
It is stirred continuously in 90 DEG C of water-baths and is evaporated liquid, 10 hours dry at 120 DEG C, 200 DEG C roast 10 hours, and SiO is made2Load
Containing 40% Tricesium dodecatungstophosphate salt catalyst, i.e. 40%Cs0.1H2.9PW12O40/SiO2。
Embodiment 4
Using the pretreated artificial synthesized silica gel of step (1) in embodiment 1.
0.302g cesium carbonate is weighed, 20ml deionized water is added, after being uniformly dissolved, impregnates the pretreated carrier of 16.0g, from
So dry in the shade, 120 DEG C drying 12 hours.
It weighs 10.66g phosphotungstic acid to be dissolved in 40ml deionized water, SiO will be modified2Dipping wherein, stands 2 hours,
It is stirred continuously in 90 DEG C of water-baths and is evaporated liquid, 10 hours dry at 120 DEG C, 200 DEG C roast 10 hours, and SiO is made2Load
Containing 40% Tricesium dodecatungstophosphate salt catalyst, i.e. 40%Cs0.5H2.5PW12O40/SiO2。
Embodiment 5
Using the pretreated artificial synthesized silica gel of step (1) in embodiment 1.
1.206g cesium carbonate is weighed, 20ml deionized water is added, after being uniformly dissolved, impregnates the pretreated carrier of 16.0g, from
So dry in the shade, 120 DEG C drying 12 hours.
It weighs 10.66g phosphotungstic acid to be dissolved in 40ml deionized water, SiO will be modified2Dipping wherein, stands 2 hours,
It is stirred continuously in 90 DEG C of water-baths and is evaporated liquid, 10 hours dry at 120 DEG C, 200 DEG C roast 10 hours, and SiO is made2Load
Containing 40% Tricesium dodecatungstophosphate salt catalyst, i.e. 40%Cs2.0H1.0PW12O40/SiO2。
Embodiment 6
Using the pretreated artificial synthesized silica gel of step (1) in embodiment 1.
0.02g ammonium chloride is weighed, 20ml deionized water is added, after being uniformly dissolved, impregnates the pretreated carrier of 16.0g, from
So dry in the shade, 120 DEG C drying 12 hours.
It weighs 10.66g phosphotungstic acid to be dissolved in 40ml deionized water, SiO will be modified2Dipping wherein, stands 2 hours,
It is stirred continuously in 90 DEG C of water-baths and is evaporated liquid, 10 hours dry at 120 DEG C, 200 DEG C roast 10 hours, and SiO is made2Load
Containing 40% Tricesium dodecatungstophosphate salt catalyst, i.e. 40% (NH4)0.1H2.9PW12O40/SiO2。
Embodiment 7
The preparation step and embodiment 3 of catalyst are consistent, and difference: the artificial synthesized silica gel in step (1) is changed to
Mesoporous silicon oxide molecular sieve SBA-15.20~40 mesh are screened out first by the powder compression molding after nitric acid pretreatment, then after being crushed
Particle preparation is at carried heteropoly acid salt catalyst, i.e. 40%Cs0.1H2.9PW12O40/SBA-15。
Embodiment 8
The preparation step and embodiment 3 of catalyst are consistent, difference are as follows: the artificial synthesized silica gel in step (1) changes
For mesoporous silicon oxide molecular sieve MCM-41.20~40 are screened out first by the powder compression molding after nitric acid pretreatment, then after being crushed
Mesh particle preparation is at carried heteropoly acid salt catalyst, i.e. 40%Cs0.1H2.9PW12O40/MCM-41。
Embodiment 9
The preparation step and embodiment 3 of catalyst are consistent, difference are as follows: the phosphotungstic acid in step (2) is changed to phosphorus molybdenum
Acid.
0.094g cesium carbonate is weighed, 20ml deionized water is added, after being uniformly dissolved, impregnates the pretreated carrier of 16.0g, from
So dry in the shade, 120 DEG C drying 12 hours.
It weighs 10.66g phosphomolybdic acid to be dissolved in 60ml deionized water, SiO will be modified2Dipping wherein, stands 2 hours,
It is stirred continuously in 90 DEG C of water-baths and is evaporated liquid, 10 hours dry at 120 DEG C, 200 DEG C roast 10 hours, and SiO is made2Load
Containing 40% phosphomolybdic acid cesium salt catalyst, i.e. 40%Cs0.1H2.9PMo12O40/SiO2。
Embodiment 10
The preparation step and embodiment 3 of catalyst are consistent, difference are as follows: the phosphotungstic acid in step (2) is changed to silicon tungsten
Acid.
0.302g cesium carbonate is weighed, 20ml deionized water is added, after being uniformly dissolved, impregnates the pretreated carrier of 16.0g, from
So dry in the shade, 120 DEG C drying 12 hours.
It weighs 10.66g silico-tungstic acid to be dissolved in 60ml deionized water, SiO will be modified2Dipping wherein, stands 2 hours,
It is stirred continuously in 90 DEG C of water-baths and is evaporated liquid, 10 hours dry at 120 DEG C, 200 DEG C roast 10 hours, and SiO is made2Load
Containing 40% silicotungstic acid cesium salt catalyst, i.e. 40%Cs0.5H3.5SiW12O40/SiO2。
Embodiment 11
The preparation step and embodiment 3 of catalyst are consistent, difference are as follows: the phosphotungstic acid in step (2) is changed to silicon molybdenum
Acid.
0.476g cesium carbonate is weighed, 20ml deionized water is added, after being uniformly dissolved, impregnates the pretreated carrier of 16.0g, from
So dry in the shade, 120 DEG C drying 12 hours.
It weighs 10.66g silicomolybdic acid to be dissolved in 60ml deionized water, SiO will be modified2Dipping wherein, stands 2 hours,
It is stirred continuously in 90 DEG C of water-baths and is evaporated liquid, 10 hours dry at 120 DEG C, 200 DEG C roast 10 hours, and SiO is made2Load
Containing 40% silicomolybdic acid cesium salt catalyst, i.e. 40%Cs0.5H3.5SiMo12O40/SiO2。
Comparative example 1
It weighs 6.86g phosphotungstic acid to be dissolved in 30ml deionized water, the 16.0g SiO that nitric acid pretreatment is crossed2Impregnate it
In, 2 hours are stood, is stirred continuously in 90 DEG C of water-baths and is evaporated liquid, 10 hours dry at 120 DEG C, 200 DEG C roast 10 hours,
SiO is made2Load contains 30% phosphotungstic acid catalyst, i.e. 30%H3PW12O40/SiO2。
Comparative example 2
It weighs 10.66g phosphotungstic acid to be dissolved in 40ml deionized water, the 16.0g SiO that nitric acid pretreatment is crossed2Impregnate it
In, 2 hours are stood, is stirred continuously in 90 DEG C of water-baths and is evaporated liquid, 10 hours dry at 120 DEG C, 200 DEG C roast 10 hours,
SiO is made2Load contains 40% phosphotungstic acid catalyst, i.e. 40%H3PW12O40/SiO2。
Comparative example 3
It weighs 10.66g phosphomolybdic acid to be dissolved in 60ml deionized water, the 16.0g SiO that nitric acid pretreatment is crossed2Impregnate it
In, 2 hours are stood, is stirred continuously in 90 DEG C of water-baths and is evaporated liquid, 10 hours dry at 120 DEG C, 200 DEG C roast 10 hours,
SiO is made2Load contains 40% phosphomolybdic acid catalyst, i.e. 40%H3PMo12O40/SiO2。
Catalytic performance of the catalyst of embodiment 1~11 and comparative example 1~3 for esterification is listed in table 2.According to implementation
The catalyst performance of example and comparative example compares and can find, provides the catalyst that technology prepares carried heteropoly acid salt according to this patent
Acetic acid conversion can be improved, or improve the selectivity of ethyl acetate selectivity or acetic acid conversion and ethyl acetate
It is all improved with space-time yield.
2 embodiment of table and comparative example catalyst prepare the catalytic performance of acetic acid ethyl reaction for ethylene and acid esterification.
Embodiment 12
It is 180 DEG C, reaction pressure 2.5MPa in reaction temperature according to catalyst made from embodiment 3, the air speed of dry gas
For 2000h-1, acetic acid feed air speed is 0.3h-1, acetic acid and ethylene molar ratio are 1:6, and acetic acid and water molar ratio are 1:0.2 condition
Under, estimation of stability experiment in 120 hours is carried out to catalyst, acetic acid conversion is shown in that Fig. 1 and ethyl acetate are selectively shown in Fig. 2.
Comparative example 4
It is 180 DEG C, reaction pressure 2.5MPa in reaction temperature according to catalyst made from comparative example 2, the air speed of dry gas
For 2000h-1, acetic acid feed air speed is 0.3h-1, acetic acid and ethylene molar ratio are 1:6, and acetic acid and water molar ratio are 1:0.2 condition
Under, estimation of stability experiment in 120 hours is carried out to catalyst, acetic acid conversion is shown in that Fig. 1 and ethyl acetate are selectively shown in Fig. 2.
It can be found by Fig. 1 and Fig. 2, the activity of carried heteropoly acid salt catalyst of the invention, selectivity and stability are bright
It is aobvious to be better than comparative example catalyst.
Claims (9)
1. a kind of method that oil refinery dry gas prepares ethyl acetate, using fixed bed reactors, in carried heteropoly acid salt catalyst
Under effect, using dilute ethylene in Oil Refinery Industry device by-product dry gas as raw material, produced with the co-feeding progress esterification of vapourised acetic acid
Ethyl acetate, it is characterised in that:
(1) using dilute ethylene in Oil Refinery Industry device by-product dry gas as raw material, dry gas may come from atmospheric and vacuum distillation, catalysis is split
One of Oil Refinery Industries device such as change, catalytic pyrolysis, thermal cracking and delayed coking or two kinds or more；
(2) the carried heteropoly acid salt catalyst, the catalyst be porous silica load phosphotungstate, silicotungstate,
Phosphomolybdate, the combination of silicomolybdate one or two or more kinds, and replace these sour hydrogen atoms counter cation K, Rb, Cs and
NH4One or more combination；
(3) reaction process condition are as follows: reaction temperature is 150~200 DEG C, and reaction pressure is 0.5~3.0MPa, the sky of dry gas
Speed is 500~5000h-1, acetic acid liquid air speed are as follows: 0.1~1.0h-1, ethylene and acetic acid molar ratio are 1:1~10；Acetic acid and water
Molar ratio is 1:0.05~1.
2. according to the method for claim 1, it is characterised in that: weight ethylene content in the raw material oil refinery dry gas are as follows: 10
~99%, sulfur content is less than or equal to 10ppm, needs not move through after desulfurization of raw material processing special purified.
3. according to the method for claim 1, it is characterised in that: the carried heteropoly acid salt catalyst, carrier are selected from more
Hole silica；Heteropoly acid is selected from Keggin-type phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid, the combination of silicomolybdic acid one or two or more kinds, and
The counter cation of these sour hydrogen atoms is replaced to be selected from K, Rb, Cs and NH with larger ionic radius4Deng it is a kind of or two kinds with
On.
4. according to the method for claim 1, it is characterised in that: the porous oxidation silicon carrier is ordered meso-porous silicon oxide
One of molecular sieve, amorphous silicon oxide, artificial synthesized silica gel or natural silica gel；Specific surface area are as follows: 50~500m2/ g is put down
Equal aperture are as follows: 6~40nm.
5. according to method described in claim 1,3 or 4, it is characterised in that: the porous silica carried heteropoly acid salt
The preparation method of catalyst: weighing potassium carbonate, rubidium carbonate, cesium carbonate, ammonium chloride one or more and be dissolved in the water, and oxidation is added
Silicon, 2~20 hours dry at 100~120 DEG C after drying in the shade naturally, the silica that must be modified；Weigh again phosphotungstic acid, silico-tungstic acid,
Phosphomolybdic acid, silicomolybdic acid one or more are dissolved in the water, and the above-mentioned silica being modified is added, and adsorb its saturation, in water-bath
It is evaporated liquid, 2~20 hours dry at 100~120 DEG C, 200~300 DEG C roast 2~10 hours.
6. according to method described in claim 1,3,4 or 5, it is characterised in that: heteropolyacid salt accounts for the carried heteropoly acid salt
10~50wt% of total catalyst weight.
7. according to method described in claim 1,3,4 or 5, it is characterised in that: the counter cation introduced by ion exchange
With the 0.05~3.0% of the heteropolyacid salt molar ratio.
8. according to the method for claim 1, it is characterised in that: reaction temperature be 160~190 DEG C, reaction pressure be 1.5~
2.5MPa, the air speed of dry gas are 1000~3000h-1, acetic acid liquid air speed are as follows: 0.2~0.8h-1, ethylene is with acetic acid molar ratio
1:2~6；Acetic acid and water molar ratio are 1:0.15~0.75.
9. according to the method for claim 1, it is characterised in that: use fixed bed reactors, ester is carried out under gas phase condition
Change reaction.
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| US5189201A (en) * | 1992-03-25 | 1993-02-23 | Showa Denko K.K. | Process for preparation of lower fatty acid ester |
| CN1483717A (en) * | 2003-06-13 | 2004-03-24 | 华南理工大学 | Process for synthesizing isopropyl acetate and method for preparing its catalyst |
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