CN106542951A - A kind of method that utilization high-efficiency adsorbent reduces alkylated reaction sulfuric acid dosage - Google Patents
A kind of method that utilization high-efficiency adsorbent reduces alkylated reaction sulfuric acid dosage Download PDFInfo
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- CN106542951A CN106542951A CN201610901119.5A CN201610901119A CN106542951A CN 106542951 A CN106542951 A CN 106542951A CN 201610901119 A CN201610901119 A CN 201610901119A CN 106542951 A CN106542951 A CN 106542951A
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- adsorbent
- acid
- moisture
- sulfuric acid
- sulphuric acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/56—Addition to acyclic hydrocarbons
- C07C2/58—Catalytic processes
- C07C2/62—Catalytic processes with acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
- C07C2527/054—Sulfuric acid or other acids with the formula H2Sn03n+1
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A kind of method that utilization high-efficiency adsorbent reduces alkylated reaction sulfuric acid dosage, the method can reduce sulphuric acid usage amount in the production isobutyltrimethylmethane. of carbon four, and method is as follows：After alkylation moisture adsorbent is dried, in adding alkylation reactor, the sulphuric acid of 98wt% is subsequently adding, carbon 4 after input dehydration is alkylated reaction at a temperature of 3 DEG C, when sulfuric acid content is measured less than 90%, stopped reaction separates spent acid and adsorbent by separating tank；Adsorbent is transported to into adsorbent reactivation workshop, qualified rear reuse is regenerated.It is an advantage of the invention that：This technique is cocatalyst by using moisture adsorbent, and adsorption moisture in course of reaction, sulphuric acid use in making isobutyltrimethylmethane. original production process reduce more than 50%, while catalyst can be used with regeneration cycle；It is process is simple, easy to operate, easy to implement, and equipment investment is few, integrated cost is low, non-secondary pollution, and economic and social benefit is notable.
Description
Technical field
The present invention relates to alkylation production cleaning procedure, reduces alkylated reaction sulphuric acid in particular with high-efficiency adsorbent and uses
The method of amount.
Background technology
Five gasoline of state will be realized cleaning tail gas, must add high-octane chemical products, synthesized environmental protection, performance and into
This factor, isobutyltrimethylmethane. are most potential additives.Calculate in the industry, to meet international standards, next year isobutyltrimethylmethane. potential need
Ask increment to be up to 8,000,000 tons, be 4 times of existing production capacity, isobutyltrimethylmethane. industry development space is huge.
The most ripe production technology of isobutyltrimethylmethane. is：The iso-butane in isobutene. and C4 in C-4-fraction, in sulfuric acid catalysis
There is alkylated reaction in the presence of agent, generate isobutyltrimethylmethane..C-4-fraction after de- lighter hydrocarbons exchanges heat to after about 11 DEG C and enters raw material
Dehydrator, the free water in C-4-fraction is separated, so that the free water content in raw material is down to 10ppm.Removing trip
Iso-butane, liquefied gas fraction from water directly mix with the circulation cryogen from flash tank and make temperature be reduced to 3.0 DEG C it is laggard
Enter C4 alkylation reactors, reaction is alkylated under sulfuric acid catalyst effect, generates isobutyltrimethylmethane..
Material moisture high one into device is to accelerate scrapping for sulfuric acid catalyst, and the Waste Sulfuric Acid amount of generation is big；Two
It is that heavy corrosion is caused to equipment.Existing technique is that, using double glazing cotton core, glass cotton core has hydrophilic, water and glass
Surface tension between cotton core is big compared with carbon four, and due to capillary difference, carbon four can comparatively fast pass through glass cotton core, and water
Slow many, small water droplet adsorbs on filtering layer surface so as to cause the coalescence of water droplet, is acted on by kinetic energy, and droplet gradually converges
Into big drop, and settle under gravity and separate with carbon four；Isobutyltrimethylmethane. per ton needs 60～80 kilogram 90% of by-product to give up
Sulphuric acid, this part Waste Sulfuric Acid contain 5% or so Organic substance, environmental protection investments and processing cost are huge, and spent acid per ton is manipulated so
This up to more than thousand yuan, the development of serious restriction industry.There is the technique without sulphuric acid such as research unit's research solid acid catalyst,
But there is not yet there is the enterprise of application.
According to the principle of sulfuric acid catalyst, the content of raw material moisture is reduced using kinds of processes or can not be stopped production and be turned
Moisture is removed, is to reduce the reasonable process for using sulfuric acid catalyst, the breakthrough of this technology has great significance.
The content of the invention
The purpose of the present invention is had problems for alkylation production, there is provided a kind of to utilize high-efficiency adsorbent transfering alkylation
The method of moisture in reaction, the method is injected capital into less, sulphuric acid can reduce more than 50% consumption, production cost significantly drops
Low, environmental burden is greatly decreased, and belongs to process for cleanly preparing.
Technical scheme：
A kind of method that utilization high-efficiency adsorbent reduces alkylated reaction sulfuric acid dosage, the method produce isobutyltrimethylmethane. in carbon four
In can reduce sulphuric acid usage amount, its step is as follows：
1), after by the drying of alkylation moisture adsorbent, in adding alkylation reactor, the sulphuric acid of 98wt%, sulfur are subsequently adding
80-150% of the addition of acid for alkylation moisture adsorbent quality, the carbon 4 after input dehydration carry out alkyl at a temperature of 3 DEG C
Change reaction, when sulfuric acid content being measured less than 90%, stopped reaction separates spent acid and adsorbent by separating tank；
2) spent acid is transported to into spent acid and processes workshop；Adsorbent is transported to into adsorbent reactivation workshop, adsorbent is in 600-
Qualified rear reuse is regenerated under the conditions of 900 DEG C, the adsorbent reactivation is qualified to refer to that adsorbent high temperature sloughs absorption water or knot
Brilliant water makes moisture less than 1wt% and decomposing organic matter；
The adsorbent be molecular sieve, anhydrous magnesium sulfate, anhydrous sodium sulfate and magnesium silicate in one or more
The mixture of meaning ratio.
The invention has the beneficial effects as follows：
This technique is cocatalyst by using moisture adsorbent, and adsorption moisture in course of reaction makes isobutyltrimethylmethane. primary
In production. art, sulphuric acid is used and reduces more than 50%, while catalyst can be used with regeneration cycle；It is process is simple, easy to operate, easy
In enforcement, and equipment investment is few, integrated cost is low, non-secondary pollution, and economic and social benefit is notable.
Specific embodiment
Further illustrate by the following examples.
Embodiment 1：
A kind of method that utilization high-efficiency adsorbent reduces alkylated reaction sulfuric acid dosage, the method produce isobutyltrimethylmethane. in carbon four
In can reduce sulphuric acid usage amount, its step is as follows：
1) concentrated sulphuric acid by 2000 kilograms of moisture less than the anhydrous sodium sulfate granule and 2000 kilograms of 98wt% of 1wt% is added
Alkylation reactor, continuously enters four raw material of carbon after dehydration, and at 3 DEG C of temperature after reaction 50 minutes, detection sulfuric acid content is
89.2wt%, stopped reaction separate spent acid and adsorbent by separating tank；
2) after separate spent acid with absorbent filtering, spent acid is transported to spent acid and processes workshop, and adsorbent is transported to adsorbent
Regeneration workshop, adsorbent oxygen enrichment regeneration 30 minutes at a temperature of 800 DEG C, detection moisture are 0.5wt%, return alkylation reactor
It is continuing with, at a temperature of this, Organic substance is decomposed into carbon dioxide and water；
Detection shows：80 kilograms of 2000 kilograms of gas washing in SA production isobutyltrimethylmethane .s, (former technique is according to isobutyltrimethylmethane. per ton for relatively former technique
Consume 60 kilograms of sulphuric acid to calculate) reduce by 60% sulphuric acid usage amount.
Embodiment 2：
A kind of method that utilization high-efficiency adsorbent reduces alkylated reaction sulfuric acid dosage, the method produce isobutyltrimethylmethane. in carbon four
In can reduce sulphuric acid usage amount, its step is as follows：
1) concentrated sulphuric acid by 2000 kilograms of moisture less than the magnesium silicate granule and 2000 kilograms of 98wt% of 1wt% adds alkyl
Change reactor, continuously enter four raw material of carbon after dehydration, at 3 DEG C of temperature after reaction 40 minutes, detection sulfuric acid content is
89.0wt%, stopped reaction separate spent acid and adsorbent by separating tank；
2) after separate spent acid with absorbent filtering, spent acid is transported to spent acid and processes workshop, and adsorbent is transported to adsorbent
Regeneration workshop, adsorbent oxygen enrichment regeneration 45 minutes at a temperature of 700 DEG C, detection moisture are 0.9wt%, return alkylation reactor
It is continuing with, at a temperature of this, Organic substance is decomposed into carbon dioxide and water.
Detection shows：68 kilograms of 2000 kilograms of gas washing in SA production isobutyltrimethylmethane .s, (former technique is according to isobutyltrimethylmethane. per ton for relatively former technique
Consume 60 kilograms of sulphuric acid to calculate) reduce sulphuric acid usage amount about 51wt%.
Embodiment 3：
A kind of method that utilization high-efficiency adsorbent reduces alkylated reaction sulfuric acid dosage, the method produce isobutyltrimethylmethane. in carbon four
In can reduce sulphuric acid usage amount, its step is as follows：
1) concentrated sulphuric acid by 2000 kilograms of moisture less than the sieve particle and 2000 kilograms of 98wt% of 1wt% adds alkyl
Change reactor, continuously enter four raw material of carbon after dehydration, at 3 DEG C of temperature after reaction 50 minutes, detection sulfuric acid content is
88.5wt%, stopped reaction separate spent acid and adsorbent by separating tank；
2) after separate spent acid with absorbent filtering, spent acid is transported to spent acid and processes workshop, and adsorbent is transported to adsorbent
Regeneration workshop, adsorbent oxygen enrichment regeneration 35 minutes at a temperature of 850 DEG C, detection moisture are 0.2wt%, return alkylation reactor
It is continuing with, at a temperature of this, Organic substance is decomposed into carbon dioxide and water.
Detection shows：78 kilograms of 2000 kilograms of gas washing in SA production isobutyltrimethylmethane .s, (former technique is according to isobutyltrimethylmethane. per ton for relatively former technique
Consume 60 kilograms of sulphuric acid to calculate) reduce sulphuric acid usage amount about 58%.
Claims (1)
1. a kind of method that utilization high-efficiency adsorbent reduces alkylated reaction sulfuric acid dosage, the method is in the production isobutyltrimethylmethane. of carbon four
Sulphuric acid usage amount can be reduced, it is characterised in that step is as follows：
1), after by the drying of alkylation moisture adsorbent, in adding alkylation reactor, the sulphuric acid of 98wt% is subsequently adding, sulphuric acid
80-150% of the addition for alkylation moisture adsorbent quality, the carbon 4 after input dehydration are alkylated at a temperature of 3 DEG C instead
Should, when sulfuric acid content is measured less than 90%, stopped reaction separates spent acid and adsorbent by separating tank；
2) spent acid is transported to into spent acid and processes workshop；Adsorbent is transported to into adsorbent reactivation workshop, adsorbent is at 600-900 DEG C
Under the conditions of regenerate it is qualified after reuse, the adsorbent reactivation is qualified to refer to that adsorbent high temperature is sloughed absorption water or water of crystallization and made
Moisture is less than 1wt% and decomposing organic matter；
The adsorbent is one or more any ratios in molecular sieve, anhydrous magnesium sulfate, anhydrous sodium sulfate and magnesium silicate
The mixture of example.
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| CN201610901119.5A CN106542951B (en) | 2016-10-14 | 2016-10-14 | A method of alkylated reaction sulfuric acid dosage is reduced using high-efficiency adsorbent |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3591655A (en) * | 1968-12-16 | 1971-07-06 | Texaco Inc | Combination of emulsion flashing and effluent refrigeration in sulfuric acid alkylation |
| US20070282150A1 (en) * | 2006-06-01 | 2007-12-06 | Randolph Bruce B | Alkylation of isobutene feeds |
| CN104151119A (en) * | 2014-08-08 | 2014-11-19 | 山东利丰达生物科技有限公司 | Method for preparing isooctane by deep processing of n-butane |
| CN105567359A (en) * | 2015-12-23 | 2016-05-11 | 裴舜尧 | Pollution-free isooctane regeneration production line |
-
2016
- 2016-10-14 CN CN201610901119.5A patent/CN106542951B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3591655A (en) * | 1968-12-16 | 1971-07-06 | Texaco Inc | Combination of emulsion flashing and effluent refrigeration in sulfuric acid alkylation |
| US20070282150A1 (en) * | 2006-06-01 | 2007-12-06 | Randolph Bruce B | Alkylation of isobutene feeds |
| CN104151119A (en) * | 2014-08-08 | 2014-11-19 | 山东利丰达生物科技有限公司 | Method for preparing isooctane by deep processing of n-butane |
| CN105567359A (en) * | 2015-12-23 | 2016-05-11 | 裴舜尧 | Pollution-free isooctane regeneration production line |
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