CN1008352B - Recovery of waste acid of sulfuric acid alkylation - Google Patents
Recovery of waste acid of sulfuric acid alkylationInfo
- Publication number
- CN1008352B CN1008352B CN 86101738 CN86101738A CN1008352B CN 1008352 B CN1008352 B CN 1008352B CN 86101738 CN86101738 CN 86101738 CN 86101738 A CN86101738 A CN 86101738A CN 1008352 B CN1008352 B CN 1008352B
- Authority
- CN
- China
- Prior art keywords
- acid
- dilute sulphuric
- sulfuric acid
- sulphuric acid
- sulfur waste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Images
Abstract
Waste acid during the sulfuric acid alkylation high-octane petrol production has the defects of malodour and severe environmental pollution. The present invention adopts a simple method for recovering and utilizing acid sludge, namely that the acid sludge is directly heated, filtered and concentrated for producing concentrated sulfuric acid. First, the acid sludge is hydrolyzed, and diluted sulfuric acid is obtained through static delamination; the diluted sulfuric acid carries out decolorization and deodorization by an activated carbon absorption method or a phenol extraction method; then, the diluted sulfuric acid is heated for concentration or is directly heated by hot carrier gas for producing concentrated sulfuric acid. During the hydrolysis delamination, polymeric coil can be obtained, and thiol can be obtained in the heating process for concentration. The sulfuric acid recovery amount of the present invention accounts for 60 to 70% of the waste acid sludge.
Description
The invention belongs to the useless vitriolic recycling that refinery's sulfuric acid process alkyl plant is discharged.
Refinery's sulfuric acid process alkylation is the important process of production high octane gasoline component.Because the recycle acid concentration in the device drops to 85% with the next industrial waste acid that becomes.Therefore every sulfuric acid alkylation plant all has number anxious pending in the spent acid of kiloton every year.Because spent acid is the mixture of a kind of composition and complicated organic sulfide and organosulfur acid complex etc., has stench, environmental pollution is serious.
The waste acid recycling method of taking both at home and abroad at present has three kinds: 1, He Miba (Ha ミ バ リ) high-temperature cracking method.Be about to spent acid and send into cracker, under about 1000 ℃ high temperature, be cracked into SO
2Gas is again with SO
2Be converted into SO
3, after water or sulfuric acid absorption, become the vitriol oil.2, Tai Ersi people's such as (Stiles) crystallization absorption method, be about to a part of round-robin alkyl acid neglect cold so that freezing, thereby extract 100% sulfuric acid crystallization out, send back to again in the sulfuric acid alkylation reactor.3. " SARP " method promptly is converted into alkyl ester to main a part of acid, and the alkylation ester that will remove impurity again sends back to alkylation reactor.
Aforesaid method is complex technical process not only, the energy consumption height, and except that He Mibafa, can't thoroughly solve recovering waste acid and utilize problem.
Purpose of the present invention is to select technological process simple, easy to operate, and the acid sludge that consumes energy low is recycled method.Improve the recovering waste acid utilization ratio, eliminate " three wastes ", protect the environment from pollution.
Content of the present invention comprises produces dilute sulphuric acid with the acid sludge hydrolysis earlier, and produces 98% the vitriol oil by dilute sulphuric acid.Now be described below:
The hydrolysis absorption method comprises two processes.
1. the hydrolysis spent acid is produced dilute sulphuric acid.
Spent acid is pumped into the hydrolysis separating tank, again with the 5-10 liter/minute speed slowly add the dilute aqueous soln of water (tap water or natural water) or soluble salt in the spent acid, the limit edged stirs (or adopting porcelain mixing tank).Add water or rare salts solution amount be that the volume ratio of spent acid and water is 1: 1.2.
Add and stop after water finishes stirring, the quiescent settling layering is about, and the upper strata accounts for 8～12% more than 4 hours, is polymerization alkylation oil.This stand oil has plasticity-, can make additive, is added in the 10# pitch, can improve the bituminous extensibility.Also can be to wherein adding a small amount of tung oil, Resins, epoxy is made paint usefulness, and it is coated with face gloss, can be water-fast, acid-and base-resisting also can act as a fuel separately.
The dilute sulphuric acid of lower floor is extracted out by the bottom of hydrolysis separating tank, owing to wherein contain multiple organic impurity, and be dark red brown, and foul smelling, can adopt two kinds of methods for making its decolouring and deodorizing:
(1) absorption method: dilute sulphuric acid is fed decolouring and deodorizing in the adsorber that granular active carbon is housed by the container bottom, or with soaking absorption method, in adsorption tanks, put into earlier 1/4 the gac that is about dilute sulphuric acid weight, introduce dilute sulphuric acid again, soak time generally more than 48 hours, gets final product decolouring and deodorizing.As heated and boiled, just can accelerate rate of adsorption greatly, as long as generally be heated to back 10 minutes of boiling, just can be with the dilute sulphuric acid deodorization and discoloration to water-white.The use of regenerating after gac uses 4-5 time.The regenerated method is: soaked 1 hour with 1: 1 acetone-alcohol blend, filter is done, and will filter gac secluding air under 400 ℃ of conditions of doing again and heat 3 hours.Waste acetone-alcohol blend can reclaim with rectification method.
(2) use the phenol extraction process, the phenol that weight is approximately dilute sulphuric acid 1/10 amount pumps in the dilute sulphuric acid, stirs while pumping into, and is then static more than 4 hours.Then layering, upper strata are phenol and extract thereof, lower floor be decolouring and deodorizing the dilute sulphuric acid of beige.Impure phenol mixes with isopyknic water, is heated to more than 70 ℃, and water and phenol dissolve each other fully, and organic impurity is oil phase and floats on solution surface, separates oil phase and solution mutually, and the solution cooling that will contain phenol is separated out phenol, and phenol and water are all reusable.
2. produced the method for 98% the vitriol oil by dilute sulphuric acid, method has two kinds:
(1) heating of the dilute sulphuric acid behind the decolouring and deodorizing is concentrated, when dilute sulphuric acid is heated to 75-95 ℃, produce a kind of yolk yellow oily liquids above, smell is very big, account for the 1-2% of dilute sulphuric acid amount, be assorted mercaptan through initial analysis, when being heated to 110 ℃ of left and right sides, dilute sulphuric acid comes to life, and this moment, its proportion was about 1.3.Be heated to about 170 ℃, moisture content is removed substantially, and this moment, acid concentration reached more than 80%, produces a large amount of bubbles in the liquid, and content roughly has about 10%.For preventing that bubble from overflowing, stop repeatedly heating four times; Or feed hot blast froth breaking about 200 ℃.Temperature rises to after 190 ℃, and foam no longer produces, and organism begins to decompose.Rise heat to about 210 ℃, begin to contain SO in the steam
3Gas, can obviously find out during to 230 ℃ has SO
3Gas steams, SO
3Gas absorbs with dilute alkaline soln by usual method.When continuing to be heated to 248 ℃, the foam completely dissolve, this moment, sulfuric acid concentration can reach 92.5%.Sulfuric acid look such as the oily prepared Chinese ink of this moment, viscosity is big, wherein contains a large amount of coke grains.Be elimination coke grain, need add water, make the coke fines bigger particle that congeals into Dilution of sulphuric acid.The amount of dilution water be sulfuric acid amount 1-1.1 doubly, the sulfuric acid concentration after the dilution is about 50%, filtration can be adopted the acid-proof ceramics strainer, filter paper get final product with common quantitative paper, during because of 50% left and right sides of sulfuric acid concentration, to the corrosion of filter paper also not quite.Filtrate is peak green, concentrates when being heated to 340 ℃, and just becoming no look transparent, and concentration reaches 98.09% the vitriol oil, also separates out white depositions in the while acid, and this throw out dissolves in dilute sulphuric acid, the gained solution usefulness of can purifying waste water.
(1) method heating concentration flow path figure as shown in Figure 1.
This method is an indirect heating, has only the glass of employing or ceramic device just can stand sulfuric acid corrosive nature at high temperature.
(2) method is to utilize warm air or purifying flue gas direct heating.Dilute sulphuric acid is pumped in the evaporating kettle that inwall is lined with graphite cake or acid-resistant porcelain, and 360 ℃-400 ℃ warm air or the stack gas Glass tubing (or vitrified pipe) in being deep into acid is passed in the still.Pipeline can not adopt nozzle, composition that also can pilot-gas.Before still temperature rise to 108 ℃, what heat-carrying gas was taken out of from still mainly is water vapor.This mixed gas is by water wash column or alkali lye (sodium hydroxide or calcium hydroxide) absorption tower, wherein with a little SO
3Gas just can be absorbed, and residual gas just can be discharged in the atmosphere.After temperature was raised to 108 ℃, sulfuric acid began decomposing H
2SO
4(△)/() H
2O+SO
3, the SO that decomposites
3Gas is taken out of by heat-carrying gas immediately.At this moment carried a large amount of SO in the heat-carrying gas
3, this gas is incorporated in the sulfuric acid absorption tower, just can draw 98% the vitriol oil.In the heat-carrying gas after absorbing only with a little SO
3, this gas is as long as just can be discharged in the atmosphere through alkali cleaning.
The schema of this method as shown in Figure 2.
List several embodiments of the present invention below:
Example 1: the dilute aqueous soln that adds entry or soluble salt in 100 milliliters of spent acid is hydrolyzed, the tap water that adds different salts solutions or different amounts to the influence of hydrolysising separating effect see Table 1, table 2.
The dilute sulphuric acid of example 2:200 gram after hydrolysis separates soaks absorption with 100 gram industrial activited carbons, as heated and boiled, can accelerate rate of adsorption greatly, and heated and boiled sees Table 3 to the influence of rate of adsorption.
Example 3: 100 gram ground phosphate rock of 27 grades are added 56 milliliters in water, mix the sposh shape, then add 80 gram spent acid, stirring reaction is produced phosphate fertilizer, and its product the results are shown in Table 3.
Table 3 phosphate fertilizer ingredient
Numbering available phosphorus free acid is (with P
2O
5Meter) % moisture content (gram)
（P
2O
5）%
1 13.99 4.41 18.03
2 14.42 3.03 15.54
3 11.59 2.48 14.24
Claims (4)
1, a kind of sulfur waste acid recovery method of sulfuric acid process alkylated reaction, it is characterized in that adding volume ratio earlier in sulfur waste acid is 1: the water of 0.5-2.5 is hydrolyzed, the limit adds the waterside and stirs, static layering again, the upper strata is a stand oil, lower floor is for containing a small amount of organic dilute sulphuric acid, with dilute sulphuric acid with active carbon adsorption or phenol extraction process decolouring and deodorizing, then be heated to 248 ℃ of cokeization, add 1-1.1 water dilution doubly again, filter, the filtrate heating is concentrated into 340 ℃, by weight, the add-on of gac is 1/4 of a dilute sulphuric acid, and the add-on of phenol is 1/10 of a dilute sulphuric acid.
2, a kind of sulfur waste acid recovery method of sulfuric acid process alkylated reaction, it is characterized in that adding volume ratio earlier in sulfur waste acid is 1: the water of 0.5-2.5 is hydrolyzed, the limit adds the waterside and stirs, static layering again, the upper strata is a stand oil, lower floor with active carbon adsorption or phenol extraction process decolouring and deodorizing, then is heated to 75-95 ℃ with dilute sulphuric acid for containing a small amount of organic dilute sulphuric acid, reclaim assorted mercaptan, reheat to 248 ℃ cokeization adds 1-1.1 water dilution doubly, filters, the filtrate heating is concentrated into 340 ℃, by weight, the add-on of gac is 1/4 of a dilute sulphuric acid, and the add-on of phenol is 1/10 of a dilute sulphuric acid.
3, a kind of sulfur waste acid recovery method of sulfuric acid process alkylated reaction, it is characterized in that in sulfur waste acid, adding earlier volume ratio 1: 0.5-2.5, weight ratio is that 1: 1.2 water is hydrolyzed, the limit adds the waterside and stirs, static layering again, the upper strata is a stand oil, lower floor is for containing a small amount of organic dilute sulphuric acid, in dilute sulphuric acid, feed 360-400 ℃ warm air or stack gas direct heating, the SO after the decomposition
3Take out of by heat-carrying gas, then absorb by sulfuric acid absorption tower.
4,, it is characterized in that the time of static layering after the sulfur waste acid hydrolysis should be more than 4 hours according to claim 1,2 or 3 described sulfur waste acid recovery methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86101738 CN1008352B (en) | 1986-03-15 | 1986-03-15 | Recovery of waste acid of sulfuric acid alkylation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86101738 CN1008352B (en) | 1986-03-15 | 1986-03-15 | Recovery of waste acid of sulfuric acid alkylation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86101738A CN86101738A (en) | 1987-03-25 |
| CN1008352B true CN1008352B (en) | 1990-06-13 |
Family
ID=4801502
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 86101738 Expired CN1008352B (en) | 1986-03-15 | 1986-03-15 | Recovery of waste acid of sulfuric acid alkylation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1008352B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172037A (en) * | 2013-03-27 | 2013-06-26 | 刘立文 | Method for decoloring sulfuric acid by using activated-carbon filter screen |
| CN105217654B (en) * | 2015-11-10 | 2017-12-15 | 天津如有科技有限公司 | Alkylation waste sulfuric acid recycling treatment device and method |
| CN105964004B (en) * | 2016-07-04 | 2018-06-29 | 中国石油化工股份有限公司 | A kind of sulfuric acid alkylation reaction product asks for the device of flash evaporation |
| CN109650368A (en) * | 2017-10-12 | 2019-04-19 | 中国科学院过程工程研究所 | A kind of organic spent acid processing method |
| CN109052338A (en) * | 2018-08-27 | 2018-12-21 | 青岛惠城环保科技股份有限公司 | A kind of processing method of the Waste Sulfuric Acid of alkylation production process discharge |
| CN109095442B (en) * | 2018-08-27 | 2022-01-11 | 青岛惠城环保科技股份有限公司 | Method for treating waste sulfuric acid discharged in alkylation production process |
| CN109485021A (en) * | 2019-01-10 | 2019-03-19 | 钦州学院 | A kind of method of thermally conductive resolution process waste sulfuric acid from alkylation |
| CN109721035B (en) * | 2019-03-18 | 2022-02-01 | 南京蓝胜环保科技有限公司 | Purification and concentration process of waste dilute sulfuric acid |
-
1986
- 1986-03-15 CN CN 86101738 patent/CN1008352B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN86101738A (en) | 1987-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102633399B (en) | Comprehensive treatment and resource utilization technology of 2-naphthol production wastewater | |
| CN101428915B (en) | Method for zero discharge processing of waste saponification lye of cyclohexanone produced by cyclohexane oxidation technology | |
| CN102079603B (en) | High-concentration organic and inorganic mixed wastewater treatment and recovery method | |
| CN102424498B (en) | Circular and comprehensive utilization method for ethylene alkali waste liquid | |
| CN103045288B (en) | Comprehensive treatment method of high-sulphur high-COD (Chemical Oxygen Demand) caustic sludge waste liquid | |
| CN1986390A (en) | Process of purifying and recovering waste sulfuric acid containing organic impurity | |
| CN1008352B (en) | Recovery of waste acid of sulfuric acid alkylation | |
| CN108117208A (en) | The processing method and processing unit of a kind of alkali residue waste liquid | |
| CN103771608B (en) | A kind for the treatment of process of refinery alkaline residue | |
| CN102442748A (en) | Deep treatment method of naphthenic acid wastewater | |
| CN1676461A (en) | Method for extracting iodine from rejected material generated during production of phosphor product from iodine-containing phosphorus ore | |
| CN103113912A (en) | Method for separating and extracting crude oil from oil sand | |
| CN103771607B (en) | The treatment process of refinery alkaline residue | |
| CN107235586B (en) | Method for treating high-salt-content denitrification sewage | |
| CN102731262A (en) | Method for recovering phenolic compounds from coal-derived oil products | |
| CN1153764A (en) | Pinene esterifying and saponifying process synthesizing borneol and composite boron-titanium based catalyst | |
| CN1254711A (en) | Process for recovering useful substances from waste liquid generated in preparing process of caprolactam | |
| CN101570714A (en) | Used oil regenerated by refining and distilling mixed alkali | |
| CN1026487C (en) | One-step salt-making process for preparing naphthenic acid dedicated to paint | |
| CN103893941B (en) | Utilize alkaline residue treatment of wastes with processes of wastes against one another neutralizing hydrolysis to process the method for organic silicon slurry slag | |
| CN105731375B (en) | Salkali waste liquid processing method, reduce carbon black method and its device | |
| CN115449421B (en) | Low-cost and high-efficiency regeneration pretreatment method for waste lubricating oil and regeneration pretreatment agent | |
| CN1081617C (en) | Method for prodn. of glycerin by using waste liquor from saponification process | |
| CN1927743A (en) | Method for processing kettle-liquid of acrylonitrile quench tower lower portion | |
| CN1029925C (en) | Method for recoverying earth wax from earth wax argil residue |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |