CN108529569A - A kind of recovery and treatment method of waste sulfuric acid from alkylation - Google Patents
A kind of recovery and treatment method of waste sulfuric acid from alkylation Download PDFInfo
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- CN108529569A CN108529569A CN201810241296.4A CN201810241296A CN108529569A CN 108529569 A CN108529569 A CN 108529569A CN 201810241296 A CN201810241296 A CN 201810241296A CN 108529569 A CN108529569 A CN 108529569A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/16—Hydrogen sulfides
- C01B17/165—Preparation from sulfides, oxysulfides or polysulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/462—Sulfates of Sr or Ba
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Abstract
The invention discloses a kind of recovery and treatment methods of waste sulfuric acid from alkylation, Waste Sulfuric Acid with vulcanized sodium react and generates hydrogen sulfide and sodium sulphate, the sodium sulphate of generation carries out metathesis reaction with barium sulphide again and generates barium sulfate and vulcanized sodium, the vulcanized sodium of generation can be reacted with Waste Sulfuric Acid again as reaction raw materials, be recycled；The hydrogen sulfide of generation is refined, dehydration and drying, high pressure compressed, is settled, re-refining to obtain finished product hydrogen sulfide by two-stage washing.When the hydrogen sulfide progress two-stage washing to generation is refined, use the mode that two kinds of method for washing are combined, the two is used in conjunction with each other, and not only can effectively be cleaned, to improve the purity of hydrogen sulfide, process is simple, equipment energy consumption is low, does not generate industrial wastewater, and intermediate product can recycle, cost is reduced, safety is higher.It is simultaneously hydrogen sulfide and barium sulfate by the final product that the present invention obtains, it is had a wide range of applications in the fields such as the raw material of auxiliary pharmaceutical adjuvant, pesticides additive agent, ore dressing, military project chemistry, paint, ink, plastics, rubber and accumulator or filler, there is very high utility value and economic benefit.
Description
Technical field
The invention belongs to technical field of environmental protection in chemical industry, and in particular to a kind of recovery and treatment method of waste sulfuric acid from alkylation.
Background technology
There are one sulfonation process when producing petroleum sodium sulfonate, barium mahogany sulfonate, calcium mahogany sulfonate, mostly use with
Sulfuric acid alkylation technique of the concentrated sulfuric acid as catalyst, alkylation are to keep iso-butane and alkene anti-under the action of strong acid catalyst
Alkylate oil should be generated.Alkylate oil octane number is high, sensibility is small, not sulfur-bearing, aromatic hydrocarbons, alkene, have ideal volatility and
Clean flammability is the ideal blend component of aviation gasoline and motor petrol.With quality of gasoline upgrading there is an urgent need to, with
And higher and higher environmental requirement, alkylated importance is increasingly prominent, but will produce a large amount of alkyl in the process
Change spent acid, be alkylated spent acid abbreviation spent acid, be a kind of colloidal liquid that viscosity is larger, color and luster is in dark red, and property is unstable
It is fixed, particularity stink is distributed, it is difficult to handle, serious pollution is brought to ecological environment.
Currently, the processing to sulfuric acid alkylation spent acid both at home and abroad, common sulfuric acid alkylation spent acid processing mainly has following
Approach：1. passing through high temperature pyrolysis industrial sulphuric acid；2. producing white carbon；3. producing ammonium sulfate.Approach 1 is warmed by high
Cracking industrial sulphuric acid processed, early stage, domestic spent acid cracker mostly used the U.S. Meng Moke of import（MECS）And Top of Denmark
Rope wet method sulfuric acid（WSA）Technology.High-temperature cracking method main technique principle：Waste sulfuric acid from alkylation is at a high temperature of 1000-1100 DEG C
SO is made in cracking2Gas, organic matter therein are combusted into as CO simultaneously2.Then by high temperature SO obtained2Furnace gas passes through waste heat
Boiler cools down, and is then delivered to sulfuric acid production system production industrial sulphuric acid, but the method is more demanding to its equipment material, technique
Flow is complex, and single system equipment investment is big, in addition cracks the SO in furnace gas3It is higher with moisture, cooling system corrosion
It is very serious.It is the work that precipitated silica and oil antirust agent are manufactured using waste sulfuric acid from alkylation to produce white carbon for approach 2
Skill route, the route is simple, small investment, and with good economic efficiency, but the technique will produce a large amount of industrial wastewaters,
Generate secondary pollution.It is the road for producing ammonium sulfate this method with ammonium hydroxide using waste sulfuric acid from alkylation to produce ammonium sulfate for approach 3
Line is simple, and equipment investment is little, but the godied oil that the technique is isolated during acid-base neutralization reaction is not handled,
It is still a kind of pollution sources, it is deep with the ammonium sulfate of spent acid production, phosphate fertilizer color, there are stronger penetrating odor, and current state
Interior nitrogenous fertilizer market has been saturated, and the ammonium sulfate made of spent acid is difficult to enter market.
Patent CN105540900A discloses a kind of method and apparatus being alkylated spent acid processing and organic phase recycling, mainly
Technique is the mechanical demulsification of progress after settling spent acid, then carries out oleic acid two-phase laminated flow, but requirement of the method to emulsion breaker
In addition height can still obtain spent acid when carrying out oleic acid two-phase laminated flow, also need to be further processed, increase treatment process, while right
Impurity in spent acid can not be handled totally, and impurity content is higher；Patent CN204151066U one kind can handle alkylation spent acid
Sulphur recovery new equipment, disclose a kind of waste sulfuric acid from alkylation and burn sulphur unit processed, spent acid and sour gas, oxygen in the patent
Gas, gas jointly enter acid gas combustor burn, when in addition sour gas or gas enter burner combustion, it is careless slightly just
Explosion may be caused, safety is to be improved.There is also common disadvantages for above-mentioned patent simultaneously, i.e., the intermediate production in processing procedure
Object can not be recycled, and caused the waste of resource, increased cost.
Invention content
The present invention provides a kind of recovery and treatment method of waste sulfuric acid from alkylation, it is multiple to solve process in background technology
Miscellaneous, equipment energy consumption is high, generates industrial wastewater, generates secondary pollution, and the intermediate product in processing procedure can not be recycled,
A series of problems, such as product utilization rate is low after processing, of high cost, and safety is poor, and impurity content is high.
Specific technical solution is as follows：
Waste Sulfuric Acid with vulcanized sodium react generating hydrogen sulfide and sulfuric acid by a kind of recovery and treatment method of waste sulfuric acid from alkylation
Sodium, the sodium sulphate of generation carries out metathesis reaction generation barium sulfate and vulcanized sodium, the vulcanized sodium of generation with barium sulphide again to be made
It reacts, recycles with Waste Sulfuric Acid again for reaction raw materials；The hydrogen sulfide of generation refined, dehydration and drying, high pressure by two-stage washing
It compresses, settle, re-refining to obtain finished product hydrogen sulfide.
Preferably, concrete operation step is as follows：
（1）Be continuously added into Waste Sulfuric Acid and vulcanized sodium into middle pressure reaction kettle, make Waste Sulfuric Acid and vulcanized sodium in middle pressure reaction kettle into
Row reaction；
（2）Hydrogen sulfide is generated during being continuously added into, it is refined to carry out two-stage washing to the hydrogen sulfide of generation first, then into
Enter seven grades of drying systems to be dehydrated, dry laggard horizontal high voltage compression, into hydrogen sulfide settling tank, after the completion of sedimentation, then
It is refined with hydrogen sulfide private filter, is filled in dedicated hydrogen sulfide liquid steel cylinder after the completion of refined；
（3）Another product that reaction generates is sodium sulphate, is entered after sodium sulphate is filtered in metathesis reaction kettle, is added
Barium sulphide is reacted, and barium sulfate and vulcanized sodium are generated；
（4）The barium sulfate of generation is filtered compression, makes barium cake, refined drying is then carried out, obtains barium sulfate finished product；
（5）By step（3）The vulcanized sodium of middle generation is added to step（1）In, continue to carry out neutralization reaction, cycle with Waste Sulfuric Acid again
It utilizes.
Preferably, the resistance to pressure pressure of medium pressure reaction kettle is 0.2-0.6MPa.
Preferably, the step（3）In when being filtered to sodium sulphate, be filtered using with flame filter press.
Preferably, a concentration of 10%-30% of vulcanized sodium that neutralization reaction occurs with Waste Sulfuric Acid.
Preferably, the two-stage washing is refined by the way of magnet ring washing, first refined with ceramic magnet ring washing, then with not
Steel magnet ring washing of becoming rusty is refined.
Preferably, hydrogen sulfide is dried by seven grades of drying systems, seven grades of drying systems include four big
Drying chamber and excessively three small drying chambers, moisture≤0.2% of dry after cure hydrogen；Below seven grades of drying systems
It is connected with vacuum refining system.
Preferably, when carrying out high pressure compressed to hydrogen sulfide, the high-pressure is 9.6-14.6MPa.
Preferably, before carrying out high pressure compressed to hydrogen sulfide, first nitrogen is passed into compressed tanks, is replaced three times.
Preferably, the sedimentation time is 24-30 hours.
Advantageous effect：
1. the present invention is by Waste Sulfuric Acid and vulcanized sodium by react generation hydrogen sulfide and sodium sulphate, the sodium sulphate of generation is again and sulphur
Change barium and carry out metathesis reaction generation barium sulfate and vulcanized sodium, the vulcanized sodium of generation can be used as reaction raw materials anti-with Waste Sulfuric Acid again
It answers, recycles, avoid wasting, reduce cost.
2. when the hydrogen sulfide progress two-stage washing to generation is refined, the mode that two kinds of method for washing are combined is used,
First use ceramic magnet ring, then with stainless steel magnet ring, ceramic magnet ring can effectively remove impurity carbon disulfide, and the magnet ring of stainless steel
To elemental sulfur, there are one suction-operateds again, and the two is used in conjunction with each other, not only can effectively clean, to improve hydrogen sulfide
Purity.
3. using the mode of seven grades of silica gel absorptions dehydration and drying, also have the function of refining while dry moisture,
Hydrogen sulfide in such a way that small drying chamber is combined, is first passed through four big drying chambers first and carried out by this step using big drying chamber
Preliminarily dried removes most moisture, and depth drying is carried out using three small drying chambers, both can be to avoid whole uses
Dry insufficient problem caused by small drier, but can to avoid all using big drier and caused by refined degree it is poor
Problem can further increase the purity of hydrogen sulfide.
4. the resistance to pressure pressure that drying laggard horizontal high voltage uses when compressing is 9.6-14.6MPa, in this pressure limit, not only
Can gaseous hydrogen sulfide be effectively converted into liquid hydrogen sulfide, and the resistance to pressure valve cost used at this time is relatively low, Ji Nengti
The conversion ratio of high gaseous hydrogen sulfide, and the problem of can prevent low-pressure from gaseous hydrogen sulfide being caused to reveal.
5. before carrying out high pressure compressed to hydrogen sulfide, first nitrogen is passed into compressed tanks, is replaced three times, sulphur is prevented
Change hydrogen to explode under high pressure with the oxygen in air, improves safety.
6. being hydrogen sulfide and barium sulfate by the final product that the present invention obtains, both final products are added in medicine
The fields such as agent, pesticides additive agent, ore dressing, military project chemistry, the raw material of paint, ink, plastics, rubber and accumulator or filler tool
It is widely used, there is very high utility value and economic benefit.
Description of the drawings
Fig. 1 is flow chart of the present invention.
Fig. 2 is seven grades of drying system schematic diagrames of the invention.
Fig. 3 is line chart of the different resistance to pressure pressures to hydrogen sulfide impurities affect.
Specific implementation mode
Two kinds of products of the present invention：Barium sulfate and hydrogen sulfide, wherein barium sulfate are with a wide range of applications, barium sulfate
Property is relatively stable, meets hydrogen sulfide in air or toxic gas is also non-discolouring, is used as paint, ink, plastics, rubber and electric power storage
The surface smears of the raw material or filler in pond, photographic pape and art paper, the sizing agent of textile industry are used as in glassware
Fining agent, can play a part of defoam and increase gloss, also can be used as the protection wallpaper of anti-radioactive ray, be additionally operable to ceramics, enamel,
The industries such as fragrance, pigment, and the raw material of other barium salts is manufactured, also it can medically make digestive system contrast agent, using very
Extensively, it has use value.
Another product hydrogen sulfide, vulcanization hydrogen production are indispensable originals in chemical field mainly as reducing agent
Material, hydrogen sulfide have a wide range of applications in fields such as auxiliary pharmaceutical adjuvant, pesticides additive agent, ore dressing, military project chemistry.More and more
Research shows that hydrogen sulfide participates in regulation and control stomatal movement, photosynthesis, kind as a kind of multi-functional plant gaseous signal molecule
Many physiology courses such as son sprouts, the developing of leaf and root organ, degeneration-resistant stress, and recently the study found that hydrogen sulfide can delay
The ripening and senscence process of a variety of fruits and vegetables is a kind of widely used compound.
Embodiment：
Clearly narration in detail is carried out to the solution of the present invention with reference to embodiment.
Embodiment 1：
The present embodiment is carried out according to following operating procedure：
（1）Waste Sulfuric Acid and vulcanized sodium are added in middle pressure reaction kettle and reacted, the resistance to pressure pressure in middle pressure reaction kettle is
0.2MPa, persistently squeezes into a concentration of 72.5% Waste Sulfuric Acid on one side, persistently squeezes into a concentration of 10% vulcanized sodium, five tons of capacity on one side
Reaction kettle, squeeze into three tons of raw material of sum, continue to be added for six hours；
（2）Hydrogen sulfide is generated during being continuously added into, carrying out two-stage washing to the hydrogen sulfide of generation first refines, first with pottery
The washing of porcelain magnet ring is refined, then is washed and refined with stainless steel magnet ring.Then hydrogen sulfide is dried by seven grades of drying systems, institute
It states drying system to include four big drying chambers and cross three small drying chambers, first passes through four big drying chambers（Volume is
1m3）, then pass through three small drying chambers（Volume is 0.5m3）, before carrying out high pressure compressed to hydrogen sulfide, first nitrogen is passed through
It into compressed tanks, is replaced, hydrogen sulfide is passed into compressed tanks three times then, the resistance to pressure pressure of compressed tanks is 9.6MPa,
After the completion of compression, into hydrogen sulfide settling tank, sedimentation for 24 hours, then with hydrogen sulfide private filter is refined, and is filled after the completion of refining
It is attached in dedicated hydrogen sulfide liquid steel cylinder, obtains liquid hydrogen sulfide finished product；
（3）Another product that reaction generates is sodium sulphate, and metathesis reaction is entered after sodium sulphate is filtered with flame filter press
In kettle, barium sulphide is added and is reacted, barium sulfate and vulcanized sodium are generated；
（4）The barium sulfate of generation is filtered compression, makes barium cake, refined drying is then carried out, obtains barium sulfate finished product；
（5）By step（3）The vulcanized sodium of middle generation is added to step（1）In, continue to carry out neutralization reaction, cycle with Waste Sulfuric Acid again
It utilizes.
Embodiment 2：
The present embodiment is carried out according to following operating procedure：
（1）Waste Sulfuric Acid and vulcanized sodium are added in middle pressure reaction kettle and reacted, the resistance to pressure pressure in middle pressure reaction kettle is
0.4MPa, persistently squeezes into a concentration of 75.9% Waste Sulfuric Acid on one side, persistently squeezes into a concentration of 15% vulcanized sodium, five tons of capacity on one side
Reaction kettle, squeeze into three tons of raw material of sum, continue to be added for six hours；
（2）Hydrogen sulfide is generated during being continuously added into, carrying out two-stage washing to the hydrogen sulfide of generation first refines, first with pottery
The washing of porcelain magnet ring is refined, then is washed and refined with stainless steel magnet ring.Then hydrogen sulfide is dried by seven grades of drying systems, institute
It states drying system to include four big drying chambers and cross three small drying chambers, first passes through four big drying chambers（Volume is
1m3）, then pass through three small drying chambers（Volume is 0.5m3）, before carrying out high pressure compressed to hydrogen sulfide, first nitrogen is passed through
It into compressed tanks, is replaced, hydrogen sulfide is passed into compressed tanks three times then, the resistance to pressure pressure of compressed tanks is 10.8MPa,
After the completion of compression, into hydrogen sulfide settling tank, 26h is settled, then refined with hydrogen sulfide private filter, is filled after the completion of refining
It is attached in dedicated hydrogen sulfide liquid steel cylinder, obtains liquid hydrogen sulfide finished product；
（3）Another product that reaction generates is sodium sulphate, and metathesis reaction is entered after sodium sulphate is filtered with flame filter press
In kettle, barium sulphide is added and is reacted, barium sulfate and vulcanized sodium are generated；
（4）The barium sulfate of generation is filtered compression, makes barium cake, refined drying is then carried out, obtains barium sulfate finished product；
（5）By step（3）The vulcanized sodium of middle generation is added to step（1）In, continue to carry out neutralization reaction, cycle with Waste Sulfuric Acid again
It utilizes.
Embodiment 3：
（1）Waste Sulfuric Acid and vulcanized sodium are added in middle pressure reaction kettle and reacted, the resistance to pressure pressure in middle pressure reaction kettle is
0.6MPa, persistently squeezes into a concentration of 78.7% Waste Sulfuric Acid on one side, persistently squeezes into a concentration of 20% vulcanized sodium, five tons of capacity on one side
Reaction kettle, squeeze into three tons of raw material of sum, continue to be added for six hours；
（2）Hydrogen sulfide is generated during being continuously added into, carrying out two-stage washing to the hydrogen sulfide of generation first refines, first with pottery
The washing of porcelain magnet ring is refined, then is washed and refined with stainless steel magnet ring.Then hydrogen sulfide is dried by seven grades of drying systems, institute
It states drying system to include four big drying chambers and cross three small drying chambers, first passes through four big drying chambers（Volume is
1m3）, then pass through three small drying chambers（Volume is 0.5m3）, before carrying out high pressure compressed to hydrogen sulfide, first nitrogen is passed through
It into compressed tanks, is replaced, hydrogen sulfide is passed into compressed tanks three times then, the resistance to pressure pressure of compressed tanks is 12.6MPa,
After the completion of compression, into hydrogen sulfide settling tank, 28h is settled, then refined with hydrogen sulfide private filter, is filled after the completion of refining
It is attached in dedicated hydrogen sulfide liquid steel cylinder, obtains liquid hydrogen sulfide finished product；
（3）Another product that reaction generates is sodium sulphate, and metathesis reaction is entered after sodium sulphate is filtered with flame filter press
In kettle, barium sulphide is added and is reacted, barium sulfate and vulcanized sodium are generated；
（4）The barium sulfate of generation is filtered compression, makes barium cake, refined drying is then carried out, obtains barium sulfate finished product；
（5）By step（3）The vulcanized sodium of middle generation is added to step（1）In, continue to carry out neutralization reaction, cycle with Waste Sulfuric Acid again
It utilizes.
Embodiment 4：
（1）Waste Sulfuric Acid and vulcanized sodium are added in middle pressure reaction kettle and reacted, the resistance to pressure pressure in middle pressure reaction kettle is
0.4MPa, persistently squeezes into a concentration of 85% Waste Sulfuric Acid on one side, persistently squeezes into a concentration of 30% vulcanized sodium on one side, five tons of capacity
Reaction kettle squeezes into the raw material of three tons of sum, continues to be added for six hours；
（2）Hydrogen sulfide is generated during being continuously added into, carrying out two-stage washing to the hydrogen sulfide of generation first refines, first with pottery
The washing of porcelain magnet ring is refined, then is washed and refined with stainless steel magnet ring.Then hydrogen sulfide is dried by seven grades of drying systems, institute
It states drying system to include four big drying chambers and cross three small drying chambers, first passes through four big drying chambers（Volume is
1m3）, then pass through three small drying chambers（Volume is 0.5m3）, before carrying out high pressure compressed to hydrogen sulfide, first nitrogen is passed through
It into compressed tanks, is replaced, hydrogen sulfide is passed into compressed tanks three times then, the resistance to pressure pressure of compressed tanks is 14.6MPa,
After the completion of compression, into hydrogen sulfide settling tank, 30h is settled, then refined with hydrogen sulfide private filter, is filled after the completion of refining
It is attached in dedicated hydrogen sulfide liquid steel cylinder, obtains liquid hydrogen sulfide finished product；
（3）Another product that reaction generates is sodium sulphate, and metathesis reaction is entered after sodium sulphate is filtered with flame filter press
In kettle, barium sulphide is added and is reacted, barium sulfate and vulcanized sodium are generated；
（4）The barium sulfate of generation is filtered compression, makes barium cake, refined drying is then carried out, obtains barium sulfate finished product；
（5）By step（3）The vulcanized sodium of middle generation is added to step（1）In, continue to carry out neutralization reaction, cycle with Waste Sulfuric Acid again
It utilizes.
In addition, needed after the completion of hydrogen sulfide drying by the moisture discharge in drying chamber, therefore the present invention is at described seven grades
It is connected with vacuum refining system below drying system, the vacuum refining system includes vacuum machine and liquid caustic soda storage tank, is being discharged
The hydrogen sulfide of sub-fraction may be discharged during moisture, if node grasps not in place, operator when artificial drainage
Member may suck hydrogen sulfide, have danger；Using present vacuum refining system, lye is added in liquid caustic soda storage tank, it can
The hydrogen sulfide that can be released together with water is neutralized, and operation difficulty is reduced, and improves safety.
Embodiment 5：Liquid hydrogen sulfide finished product detection
Liquid hydrogen sulfide finished product obtained in embodiment 1-4 is detected, experimental result is as shown in table 1：
Table 1：Hydrogen sulfide purity detecting
As can be seen from the above table, liquid hydrogen sulfide made from the preparation process flow according to embodiment 3, purity highest are
99.95%, the pressure of middle pressure reaction kettle is 0.6MPa at this time, and the pressure of sedimentation time 28h, high pressure compressed are 12.6MPa, but
It is that the purity of the finally obtained liquid hydrogen sulfide of each embodiment is all higher than 99.9%, purity is higher.
Embodiment 6：Difference washing refines influence of the mode to liquid hydrogen sulfide purity
When the hydrogen sulfide progress two-stage washing to generation is refined, the mode that two kinds of method for washing are combined is used, first with pottery
Porcelain magnet ring, then with stainless steel magnet ring, ceramic magnet ring can effectively remove carbon disulfide, and the magnet ring of stainless steel is to impurity simple substance
Again there are one suction-operated, the two is used in conjunction with each other, not only can effectively clean sulphur, can improve the pure of hydrogen sulfide
Degree.
Two contrast tests are carried out in the present embodiment.Except two-stage wash purification step in addition to, other steps, parameter with implementation
Example 3 is identical, and when two-stage washing is refined wherein in contrast experiment 1 all in such a way that ceramic magnet ring washing is refined, contrast experiment 2
It is middle that the mode of refining all is washed using stainless steel magnet ring, after experiment, liquid hydrogen sulfide is detected, experimental result such as table
Shown in 2.
Table 2：Difference washing refines influence of the mode to liquid hydrogen sulfide purity
As can be seen from the above table, when carrying out washing refined, the side that is combined using ceramic magnet ring and stainless steel magnet ring
Formula, the purity highest of hydrogen sulfide；All using ceramic magnet ring in contrast experiment 1, it can be seen that the purity of hydrogen sulfide is apparent
It reducing, the content of moisture and carbon disulfide does not have significant change, but the content of simple substance sulphur impurity is to obviously increase,
Reach 2.13%；All using stainless steel magnet ring in contrast experiment 2, the purity of hydrogen sulfide is reduced compared to embodiment 3
It is more apparent, but in the component of impurity, the content of carbon disulfide is higher, is 2.4%, simple substance sulfur content is increased slightly.Thus
As it can be seen that refining mode with the two-stage washing that stainless steel magnet ring is combined using ceramic magnet ring, impure lower hydrogen sulfide is obtained.
Embodiment 7：Influence of the different dehydration and drying modes to liquid hydrogen sulfide purity
Two contrast tests are carried out in the present embodiment.In addition to dehydrating step, other steps, parameter are same as Example 3,
All using seven big drying chambers when being dehydrated wherein in contrast experiment 1, i.e. content volume is 1m3, take off in contrast experiment 2
All using seven small drying chambers when water is dried, i.e. content volume is 0.5m3, after experiment, liquid hydrogen sulfide is carried out
Detection, experimental result are as shown in table 3.
Table 3：Influence of the different dehydration and drying modes to liquid hydrogen sulfide purity
In embodiment 3, hydrogen sulfide is first passed through into four big drying chambers and carries out preliminarily dried, remove most moisture, then
Depth drying is carried out by three small drying chambers, the purity of hydrogen sulfide is 99.95% at this time, and seven are used in contrast experiment 1
Big drying chamber is dried, moisture 0.01%, but the content of its impurity elemental sulfur and carbon disulfide but obviously increases
It is high；It is dried using seven small drying chambers in contrast experiment 2, as can be seen from the table, elemental sulfur and carbon disulfide contain
Amount is on the whole roughly the same compared with the content of elemental sulfur and carbon disulfide in embodiment 3, slightly fluctuates, but moisture
Content increases apparent, it can be seen that, the present invention uses 1m3Drying chamber and 0.5m3The mode that is combined of drying chamber, not only may be used
With efficient drying, moreover it is possible to play good impurity-eliminating effect.
Embodiment 8：Influence of the different compression pressures to vulcanization hydrogen purity.
Contrast experiment is arranged in the present embodiment, and technological operation step is same as Example 3, is compressed with the laggard horizontal high voltage of drying
When compressed tanks resistance to pressure pressure be variable, carry out Comparative experiment A, B, C, D, E, wherein resistance to pressure pressure be respectively 9.6MPa,
10.6MPa, 11.6MPa, 13.6MPa, 14.6MPa, after detect hydrogen sulfide purity, the results are shown in Table 4.
| Project | Resistance to pressure pressure（MPa） | Vulcanize hydrogen purity（%） |
| Embodiment 3 | 12.6 | 99.95 |
| Test A | 9.6 | 98.35 |
| Test B | 10.6 | 98.62 |
| Test C | 11.6 | 99.04 |
| Test D | 13.6 | 99.00 |
| Test E | 14.6 | 98.17 |
As can be seen from the above table, in 9.6-12.6MPa, with the rising of the resistance to pressure pressure of compressed tanks, hydrogen sulfide it is pure
Degree also increases, and rises to 99.95% from 98.62%, reaches peak in 12.6MPa, continues the pressure for increasing compressed tanks, sulphur
The purity for changing hydrogen also declines therewith, this shows under the pressure condition of this 12.612.6MPa so that can have between hydrogen sulfide molecule
Effect association, impurity molecule therein are preferably detached with hydrogen sulfide realization, and to reduce the content of impurity, it is pure to improve hydrogen sulfide
Degree.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this profession
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification
For the equivalent embodiment of equivalent variations, as long as be without departing from technical solution of the present invention content, according to the technical essence of the invention,
Within the spirit and principles in the present invention, to any simple modification, equivalent replacement and improvement etc. made by above example, still
Belong within the protection domain of technical solution of the present invention.
Claims (10)
1. a kind of recovery and treatment method of waste sulfuric acid from alkylation, it is characterised in that：Waste Sulfuric Acid is carried out with vulcanized sodium to react generation
Hydrogen sulfide and sodium sulphate, the sodium sulphate of generation carry out metathesis reaction with barium sulphide again and generate barium sulfate and vulcanized sodium, generation
Vulcanized sodium can be reacted with Waste Sulfuric Acid again as reaction raw materials, be recycled；The hydrogen sulfide of generation is refined, de- by two-stage washing
Water drying high pressure compressed, settles, re-refines to obtain finished product hydrogen sulfide.
2. the recovery and treatment method of waste sulfuric acid from alkylation as described in claim 1, it is characterised in that：Concrete operation step is such as
Under：
（1）Be continuously added into Waste Sulfuric Acid and vulcanized sodium into middle pressure reaction kettle, make Waste Sulfuric Acid and vulcanized sodium in middle pressure reaction kettle into
Row reaction；
（2）Hydrogen sulfide is generated during being continuously added into, it is refined to carry out two-stage washing to the hydrogen sulfide of generation first, then into
Enter seven grades of drying systems to be dehydrated, dry laggard horizontal high voltage compression, into hydrogen sulfide settling tank, after the completion of sedimentation, then
It is refined with hydrogen sulfide private filter, is filled in dedicated hydrogen sulfide liquid steel cylinder after the completion of refined；
（3）Another product that reaction generates is sodium sulphate, is entered after sodium sulphate is filtered in metathesis reaction kettle, is added
Barium sulphide is reacted, and barium sulfate and vulcanized sodium are generated；
（4）The barium sulfate of generation is filtered compression, makes barium cake, refined drying is then carried out, obtains barium sulfate finished product；
（5）By step（3）The vulcanized sodium of middle generation is added to step（1）In, continue to carry out neutralization reaction, cycle with Waste Sulfuric Acid again
It utilizes.
3. the recovery and treatment method of waste sulfuric acid from alkylation as claimed in claim 2, it is characterised in that：Medium pressure reaction kettle
Resistance to pressure pressure is 0.2-0.6MPa.
4. the recovery and treatment method of waste sulfuric acid from alkylation as claimed in claim 2, it is characterised in that：The step（3）In it is right
When sodium sulphate is filtered, it is filtered using with flame filter press.
5. the recovery and treatment method of waste sulfuric acid from alkylation as claimed in claim 1 or 2, it is characterised in that：Described and Waste Sulfuric Acid
A concentration of 10%-30% of vulcanized sodium of neutralization reaction occurs.
6. the recovery and treatment method of waste sulfuric acid from alkylation as claimed in claim 1 or 2, it is characterised in that：The two-stage washing
It refines by the way of magnet ring washing, first uses ceramic magnet ring washing to refine, then washed and refined with stainless steel magnet ring.
7. the recovery and treatment method of waste sulfuric acid from alkylation as claimed in claim 1 or 2, it is characterised in that：Hydrogen sulfide is passed through
Seven grades of drying systems are dried, and seven grades of drying systems include three small drying chambers of four big drying chambers and mistake,
Moisture≤0.2% of dry after cure hydrogen；It is connected with vacuum refining system below seven grades of drying systems.
8. the recovery and treatment method of waste sulfuric acid from alkylation as claimed in claim 1 or 2, it is characterised in that：To hydrogen sulfide into
When horizontal high voltage compresses, the high-pressure is 9.6-14.6MPa.
9. the recovery and treatment method of waste sulfuric acid from alkylation as claimed in claim 1 or 2, it is characterised in that：To hydrogen sulfide into
Before horizontal high voltage compression, first nitrogen is passed into compressed tanks, is replaced three times.
10. the recovery and treatment method of waste sulfuric acid from alkylation as claimed in claim 1 or 2, it is characterised in that：The sedimentation time
It is 24-30 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113736999A (en) * | 2021-09-10 | 2021-12-03 | 山东国大黄金股份有限公司 | Method for cooperatively treating arsenic-silver-containing concentrate and waste acid by using sodium sulfide waste residues |
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| CN1046141A (en) * | 1989-04-03 | 1990-10-17 | 谭钟 | Manufacturing process of caustic soda by using of mirabilite heating method |
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| CN113736999B (en) * | 2021-09-10 | 2022-09-27 | 山东国大黄金股份有限公司 | Method for cooperatively treating arsenic-silver-containing concentrate and waste acid by using sodium sulfide waste residues |
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