CN1169710C - Process for preparing hydrogen sulfide - Google Patents
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- CN1169710C CN1169710C CNB011344571A CN01134457A CN1169710C CN 1169710 C CN1169710 C CN 1169710C CN B011344571 A CNB011344571 A CN B011344571A CN 01134457 A CN01134457 A CN 01134457A CN 1169710 C CN1169710 C CN 1169710C
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Abstract
The present invention relates to a method for producing hydrogen sulphide, which is characterized in that aqueous solution containing sulphuric acid and harmful organic matters (which is accessorily produced when organic products and intermediate products are synthesized) and calcium sulfide roasting bodies(which are prepared by hot reduction by calcium sulphate) are used as initial production materials for producing hydrogen sulphide gas. The produced hydrogen sulfide gas can be further made into other products of chemical industry. Calcium sulphate accessorily produced can be made into required calcium sulfide roasting bodies for circular use or can be made into industrial gypsum by a hot reduction method. The method can solve the problem of the effective use of the waste liquid containing sulfur acid, and favorable environmental benefit and definite economic benefit can be provided.
Description
Technical Field
The invention is a process for producing hydrogen sulfide. The technical field of the invention belongs to inorganic chemistry.
Technical Field
There are many methods for producing hydrogen sulfide, and among them, the methods closely related to the method of the present invention mainly include:
1. the invention relates to a method for producing hydrogen sulfide, which is a Chinese patent ZL 981010808.41998. The method is to produce hydrogen sulfide by reacting the waste sulfuric acid solution which is a byproduct in the production process of aromatic intermediate with sodium sulfide aqueous solution or aqueous slurry liquid which is prepared by sodium sulfide roasting body (prepared by thermal reduction of anhydrous sodium sulfate).
2. U.S. patent No. US 2,856,2671958 for recovery of hydrogen sulfide from waste acid. The acid used in the method is waste acid which is a byproduct in the processing and refining of petroleum fractions or coal tar fractions, and the sulfide used in the method can be sodium sulfide and calcium sulfide. The calcium sulfide may be an anhydrous hot calcium sulfide calcined body prepared by thermal reduction of calcium sulfate, and if the calcium sulfide calcined body contains too much carbonaceous residue, the calcium sulfide calcined body may be slurried with water to form a fine suspension, which is then separated from the carbonaceous material by clarification or filtration.
3. Processing of sulphur-containing compounds obtained from flue gas desulphurisation or recovery of calcium-containing compounds from related sources, world patent WO 99/501801999, us application. The invention relates to a method for preparing calcium sulfide containing H2Leaching the S solution to form a solution containing Ca (SH)2Removing insoluble substances, and introducing CO2By carbonation of H2S is reoxidized to elemental sulfur.
4. A method for reducing desulfurized waste residue, phosphogypsum or natural gypsum is disclosed in Chinese patent CN 1203833A 1998. The patent of the invention relates to the preparation of a suspension of the calcium sulphide calcine obtained and then the introduction of carbon dioxide into it to obtain calcium carbonate and hydrogen sulphide.
5. Hydrolysis of calcium sulphide, Brazilian patent BR 8106, 761, 1982. This invention relates to the treatment of calcium sulfide by hydrolysis to obtain H2S, adding sucrose and NH into the solution4Cl, formic acid, acetic acid, ethylenediaminetetraacetic acid and salts of the above acids, and then carbonating the solution to evolve H2S，And generates CaCO3。
6. Hydrogen sulfide from reduction of gypsum, Biswas, s.c. etc. fert.technol.1976, 13(4) 255-8. This paper relates to CO control2Flow rate, bubble size and slurry height, such that 95% of S in the aqueous suspension containing CaS is present as H2Recovery of S in the form of almost theoretical amounts of CO2The sulphur content of the sulphide in the residue was<1%.
7. Chinese patent CN 1220967A1999 of the invention of glauberite for producing sodium sulfide. The invention relates to a method for preparing sodium sulfide, which comprises the steps of carrying out thermal reduction on glauber salt ore powder, leaching a reduced substance with mirabilite water containing 10-45% of sodium sulfate, filtering, and evaporating and concentrating clear liquid to obtain a finished product of sodium sulfide.
Disclosure of Invention
The purpose of the invention is: the aqueous solution (the by-product in the production process of synthesizing organic chemical products and intermediate products by chemical reaction) containing sulfuric acid and harmful organic matters (hereinafter referred to as sulfuric acid-containing waste liquid) is effectively utilized,and the method has good environmental benefit and certain economic benefit.
The content of the invention is as follows: the hydrogen sulfide is produced by using the sulfuric acid-containing waste liquid and a calcium sulfide roasted body (prepared by thermal reduction of calcium sulfate) as starting raw materials.
In addition, acidic substances such as organic sulfonic acid, organic acid sulfate, organic carboxylic acid, hydrochloric acid, nitric acid, phosphorous acid, and phosphoric acid, which may be contained in the sulfuric acid-containing waste liquid, also react with the sulfide phase to generate hydrogen sulfide gas.
The hydrogen sulfide gas produced according to the invention can be produced into liquid hydrogen sulfide by a freezing and pressurizing liquefaction method after being output through a pipeline, or can be directly used for further processing (or after passing through a buffer gas tank) into other chemical products (such as elemental sulfur, sodium sulfide, sodium hydrosulfide, ammonium sulfide, ammonium hydrosulfide, thiourea, methyl mercaptan, ethanethiol, dimethyl sulfide, dimethyl sulfoxide and the like) without liquefaction, and can also be used as a reducing agent.
The sulfuric acid-containing waste liquid used in the invention can be obtained from the following production processes:
benzene is sulfonated and nitrified in sulfuric acid to prepare a sodium nitrobenzene sulfonate isomer mixture (dye-resistant salt S);
sulfonating and nitrifying toluene in sulfuric acid to prepare 3-nitro-4-methylbenzenesulfonic acid or sodium salt;
sulfonating, chlorinating and nitrifying toluene in sulfuric acid to prepare 2-nitro-4-methyl-5-chlorobenzene sulfonic acid or sodium salt;
sulfonating and nitrifying chlorobenzene in sulfuricacid to prepare 3-nitro-4-chlorobenzene sulfonic acid or sodium salt;
sulfonating nitrobenzene in fuming sulfuric acid to prepare m-nitrobenzenesulfonic acid or sodium salt;
sulfonating o-nitrotoluene with fuming sulfuric acid to prepare 3-nitro-4-methylbenzenesulfonic acid or sodium salt;
sulfonating p-nitrotoluene with fuming sulfuric acid to prepare 5-nitro-2-methylbenzenesulfonic acid or sodium salt;
sulfonating p-nitrochlorobenzene by fuming sulfuric acid to prepare 2-chloro-5-nitrobenzenesulfonic acid or sodium salt;
sulfonating m-aminobenzene sulfonic acid with fuming sulfuric acid to prepare 2-aminobenzene-1, 4-disulfonic acid monosodium salt;
sulfonating N-ethyl-2-methylaniline with fuming sulfuric acid to prepare 3- (N-ethyl) amino-4-methylbenzenesulfonic acid;
naphthalene is nitrified in a sulfuric acid medium to prepare 1-nitronaphthalene; 1, 5-and 1, 8-dinitronaphthalene are prepared by dinitration;
low-temperature sulfonating and nitrifying naphthalene in sulfuric acid to prepare a mixture of 1-nitronaphthalene-5-sulfonic acid and 1-nitronaphthalene-8-sulfonic acid (or sodium salt and magnesium salt thereof);
high-temperature sulfonating naphthalene in sulfuric acid, and nitrifying to obtain mixture of 1-nitronaphthalene-6-sulfonic acid and 1-nitronaphthalene-7-sulfonic acid (or their sodium salt and magnesium salt);
low-temperature disulfonating naphthalene with fuming sulfuric acid to prepare naphthalene-1, 5-disulfonic acid disodium salt and naphthalene-1, 6-disulfonic acid disodium salt;
low-temperature disulfonating and nitrifying naphthalene in fuming sulfuric acid to prepare 3-nitronaphthalene-1, 5-disulfonic acid dimagnesite;
sulfonating 2-naphthol with sulfuric acid to obtain 2-naphthol-6-sodium sulfonate;
the 2-naphthol is sulfonated by fuming sulfuric acid to prepare 2-naphthol-6, 8-disulfonic acid dipotassium salt (or ammonium potassium salt) and 2-naphthol-3, 6-disulfonic acid disodium salt;
sulfonating 2-aminonaphthalene-1-sulfonic acid with fuming sulfuric acid to prepare 2-aminonaphthalene-5, 7-disulfonic acid or monosodium salt;
naphthalene reacts with sulfuric acid and butanol to prepare sodium dibutylnaphthalenesulfonate (nekal BX);
naphthalene reacts with sulfuric acid and formaldehyde to prepare a naphthalenesulfonic acid-formaldehyde condensate (a diffusant N);
1-methylnaphthalene reacts with sulfuric acid and formaldehyde to prepare a 1-methylnaphthalene sulfonic acid-formaldehyde condensate (a dispersing agent MF);
dehydrating and cyclizing 2-benzoylbenzoic acid in sulfuric acid to prepare anthraquinone;
dehydrating and cyclizing 2- (4' -ethylbenzoyl) benzoic acid in sulfuric acid to prepare 2-ethyl anthraquinone;
2- (4' -chlorobenzoyl) benzoic acid is dehydrated and cyclized in sulfuric acid to prepare 2-chloroanthraquinone;
dehydrating and cyclizing phthalic anhydride and hydroquinone (or p-chlorophenol) in sulfuric acid to prepare 1, 4-dihydroxy anthraquinone;
the anthraquinone is nitrified in a sulfuric acid medium to prepare 1-nitroanthraquinone;
anthraquinone reacts with zinc powder (or iron powder) and glycerol in a sulfuric acid medium to prepare benzanthrone;
brominating the benzanthrone in a dilute sulfuricacid medium to prepare 3-bromobenzanthrone; dibromination is carried out to prepare 3, 9-dibromobenzanthrone;
sulfonating and brominating 1-aminoanthraquinone in fuming sulfuric acid to prepare 1-amino-4-bromoanthraquinone-2-sulfonic acid;
reacting castor oil with sulfuric acid to prepare sulfated castor oil;
reacting the butyl ricinoleate with sulfuric acid to prepare butyl ricinoleate sulfate;
reacting butyl oleate with sulfuric acid to prepare butyl oleate sulfate;
benzene reacts with chlorosulfonic acid to prepare benzene sulfonyl chloride;
reacting toluene with chlorosulfonic acid to prepare ortho-position and para-position methyl benzene sulfonyl chloride;
reacting chlorobenzene with chlorosulfonic acid to prepare p-chlorobenzene sulfonyl chloride;
reacting nitrobenzene with chlorosulfonic acid to prepare m-nitrobenzenesulfonyl chloride;
reacting o-nitrotoluene with chlorosulfonic acid to prepare 4-methyl-3-nitrobenzenesulfonyl chloride;
2-chloro-5-nitrobenzenesulfonic acid sodium salt reacts with chlorosulfonic acid to prepare 2-chloro-5-nitrobenzenesulfonyl chloride;
reacting acetanilide with chlorosulfonic acid to prepare p-acetamido benzenesulfonyl chloride.
In addition to the above production process, the sulfuric acid-containing waste liquid may be other by-products (in the production process of synthesizing organic chemical products and intermediates by chemical reaction and in the refining process). The method can be carried out by using one sulfuric acid-containing waste liquid alone or by using a plurality of sulfuric acid-containing waste liquids after being collectively mixed.
Considering that the sulfuric acid-containing waste liquid contains H2SO4In addition, the sulfur-containing waste liquid contains acidic substances such as organic sulfonic acid, organic carboxylic acid, organic acidic sulfate, hydrochloric acid, nitric acid, phosphorous acid and phosphoric acid which can react with sulfide to generate hydrogen sulfide gas, and the total content of the acidic substances in the sulfur-containing waste liquid is expressed by the total acid content, that is, the contained acids are converted into H according to the acid equivalent2SO4Number of moles or mass. The total acidity of the sulfuric acid-containing waste liquid refers to that a sample of the sulfuric acid-containing waste liquid is neutralized and titrated by a standard sodium hydroxide aqueous solution according to H2SO4Reduced acidity. The total acidity of the sulfuric acid-containing waste liquid may be (0.40-11.00) mol/L, (0.04-0.81) mol/100g or (4-80) g/100 g.
When the sulfuric acid-containing waste liquid contains a large amount of oxidizing impurities (e.g., nitric acid, chromic acid, chlorine, bromine, etc.), an appropriate amount of an inexpensive reducing substance (e.g., iron powder, urea, etc.) may be added to destroy the oxidizing impurities, and then the sulfuric acid-containing waste liquid is used in the method of the present invention.
The calcium sulfide calcined body used in the present invention is obtained by thermal reduction of various cheap calcium sulfates (for example, calcium sulfate by-produced by the method of the present invention, calcium sulfate by-produced in the processing of phosphate rock, calcium sulfate by-produced in the production of synthetic organic chemical products and intermediates, and various natural gypsums) with a reducing agent (coal powder, coke powder, various kinds of coal gas, natural gas, carbon monoxide, hydrogen gas, or the like).
The calcium sulfide roasting body can be pulped by water (clear water or wastewater with the pH value of more than 3 discharged in chemical production) to prepare water slurry containing calcium sulfide which is directly used for reacting with sulfuric acid-containing waste liquid to generate hydrogen sulfide gas.
Theoretically，1mol H2SO4Consuming 1mol CaS to yield 1mol H2S, but actually, besides the acidic substances, the sulfuric acid-containing waste liquid may also contain oxidative impurities (such as nitric acid, chromic acid, chlorine and bromine) capable of consuming CaS, and the calcium sulfide water slurry may also consume H2SO4Such as calcium hydroxide, calcium carbonate, calcium sulfite, iron oxide, aluminum oxide, silicate, etc. The reaction conditions when hydrogen sulfide gas is generated may be: the mole number of the total acid in the sulfuric acid-containing waste liquid (the acid equivalent of each acid is converted into H)2SO4) The molar ratio of the calcium sulfide to the CaS in the calcium sulfide aqueous slurry is 1: 0.70-1.25, and the molar content of the CaS in the calcium sulfide aqueous slurry is 0.70-4.20 mol/L of the slurry. The reaction temperature is 20-100 ℃; the operating pressure is 0.08-0.30 MPa.
When the calcium sulfide aqueous slurry is used, the hydrogen sulfide gas generated by the reaction of the calcium sulfide aqueous slurry with the sulfuric acid-containing waste liquid may contain impurities such as carbon dioxide and sulfur dioxide, and the calcium sulfate as a byproduct may contain impurities such as coal dust, silicate, iron sulfide, and the like.
In order to produce high-purity hydrogen sulfide gas and by-producecalcium sulfate with relatively high purity, 5-30% excess hydrogen sulfide gas can be introduced into calcium sulfide aqueous slurry to convert water-insoluble calcium sulfide (and calcium hydroxide) into water-soluble calcium hydrosulfide, and insoluble impurities can be removed by filtration. Then the calcium hydrosulfide aqueous solution and the sulfuric acid-containing waste liquid are reacted to generate hydrogen sulfide gas.
When H is present2SO4And Ca (SH)2In the reaction, 1mol of H2SO4Theoretically consuming 1mol Ca (SH)2To yield 2mol of H2S, but minus Ca (SH) produced by CaS21mol of H consumed2S, each time1mol H2SO4It is still theoretical that 1mol of H is produced2S。
H introduced into calcium sulfide water slurry2S, it is also possible to dispense with the high purities produced according to the inventionDegree H2S, instead of the low-purity H (by-product of the pesticide industry or by-product of desulfurization in the petroleum industry)2S。
The reaction conditions for preparing the calcium hydrosulfide aqueous solution by absorbing hydrogen sulfide gas by the calcium sulfide aqueous slurry liquid can be as follows: CaS and H2The mol ratio of S is 1: 1.05-1.30 (excess 5% -30%), the temperature is 20-70 ℃, the operation pressure is 0.09-0.15 MPa, and the reactor can be used for single-groove absorption or multi-groove series absorption.
The reaction conditions when the sulfuric acid-containing waste liquid reacts with the calcium hydrosulfide aqueous solution to generate hydrogen sulfide gas can be as follows: molar ratio of total acids in the sulfuric acid-containing waste liquid to Ca (SH) in the calcium hydrosulfide aqueous solution2The molar ratio of (A) to (B) is 1: 0.90 to 1.25. Ca (SH) in aqueous calcium hydrosulfide solution2The molar content (0.70-4.20) mol/L of the aqueous solution. The reaction temperature is 20-100 ℃, and the operation pressure is 0.08-0.30 MPa.
In order to avoid introducing hydrogen sulfide gas into the calcium sulfide aqueous slurry, the calcium sulfide calcined body (a by-product during synthesis of organic chemical products and intermediate products) used may be a waste liquid containing sodium sulfate (and ammonium sulfate, potassium sulfate) to cause the following reactions:
filtering the leaching solution, and separating insoluble substances to obtain the sodium sulfide-containing aqueous solution. Then the sodium sulfide-containing aqueous solution and the sulfuric acid-containing waste liquid react to generate hydrogen sulfide gas and a byproduct sodium sulfate-containing waste liquid.
The sodium sulfate-containing waste liquid can be a byproduct in the production process (and other production processes) of the following synthetic organic chemical products and intermediate products:
oxidizing and salting out 2-methyl-5-nitrobenzenesulfonic acid to prepare 4, 4 '-dinitrostilbene-2, 2' -disulfonic acid disodium salt;
high-temperature sulfonation neutralization salting-out of naphthalene prepares 2-sodium naphthalene sulfonate;
low-temperature disulfonation of naphthalene to produce naphthalene-1, 5-disulfonic acid disodium salt, naphthalene-1, 6-disulfonic acid disodium salt, and the like.
In addition, the waste liquid containing sodium sulfate which is a byproduct of the invention can also be used.
One waste liquid containing sodium sulfate can be used independently, and a plurality of waste liquids containing sodium sulfate can be mixed for use.
The pH value of the used sodium sulfate-containing waste liquid is more than 3, and SO4 ＝Ion content (0.35E ℃2.80) g-ion/L. The main reaction conditions for leaching may be: SO in waste liquid containing sodium sulfate4 ＝The gram ion number of (A) and S in the calcium sulfide calcined body used＝The ratio of gram ions of (A) to (B) is 1: 0.8 to 1.05, and the temperature is 20 to 70 ℃. S in sodium sulfide water solution after leaching and filtering＝The content (0.35-2.80) g-ion/L.
The main reaction conditions for producing hydrogen sulfide gas by the reaction of the sulfuric acid-containing waste liquid and the prepared sodium sulfide aqueous solution can be as follows: the mole number of the total acid in the sulfuric acid-containing waste liquid and the S in the sodium sulfide aqueous solution＝The ratio of total gram ions is 1: 0.7-1.20, the reaction temperature is 20-100 ℃, and the operation pressure is 0.08-0.30 MPa.
When the sulfuric acid-containing waste liquid reacts with the calcium sulfide water slurry or the calcium hydrosulfide water solution, the residual liquidcan be used for recovering the by-product calcium sulfate by a filtration method after hydrogen sulfide gas escapes. If the sulfuric acid-containing waste liquid contains soluble sulfate (such as sodium sulfate, ammonium sulfate, magnesium sulfate, aluminum sulfate, manganese sulfate, copper sulfate and the like), after hydrogen sulfide gas escapes, a proper amount of cheap or waste calcium-containing compounds such as calcium carbonate, calcium oxide, calcium hydroxide, calcium chloride or organic calcium sulfonate can be added into the residual liquid or the filtrate after calcium sulfate is filtered out, so that sulfate negative ions are all converted into water-insoluble calcium sulfate, and the recovery amount of the calcium sulfate is increased. For example:
if the sulfuric acid-containing waste liquid contains acidic substances such as organic sulfonic acid, organic carboxylic acid or hydrochloric acid, after the hydrogen sulfide gas is generated, the waste liquid containing soluble sulfate can be added into the residual liquid or the filtrate after the calcium sulfate is filtered out, so that the calcium sulfonate, the calcium carboxylate or the calcium chloride in the residual liquid or the filtrate can be converted into water-insoluble calcium sulfate to recover the calcium sulfate. For example
The by-product calcium sulfate wet filter cake can be used for preparing a calcium sulfide roasted body by thermal reduction after being dried. In addition, the wet filter cake can also be mixed with a proper amount of coal powder, extruded to be made into a hollow small cylinder, a solid small cylinder or a small ball, dehydrated at 100-200 ℃, and then used for thermal reduction to prepare a calcium sulfide roasting body so as to reduce dust. In order to save energy consumption and reduce the temperature of calcium sulfate thermal reduction, a proper amount of catalyst, such as oxides or sulfates of iron, manganese, nickel, magnesium and sodium, can be added into the calcium sulfate by-produced in the invention. In addition, the by-product calcium sulfate can also be used for manufacturing industrial gypsum.
R in the formula represents a carbon chain, a benzene ring or a naphthalene ring; the carbon chain, benzene ring or naphthalene ring may have various substituents (for example, alkyl group, halogen group, nitro group, amido group, sulfonic acid group, alkoxy group, carboxyl group or carboxyl ester group, etc.). When the filtrate obtained after the calcium sulfate filtration contains more organic sodium sulfonate, the organic sodium sulfonate can be recovered.
When the sulfuric acid-containing waste liquid reacts with the sodium sulfide aqueous solution prepared by the invention, the residual liquid containing sodium sulfate can be reused for preparing the sodium sulfide aqueous solution with the calcium sulfide aqueous slurry phase reaction after the sodium sulfide hydrogen gas escapes.
The operation of generating hydrogen sulfide gas may be a batch operation, a semi-continuous operation, or a continuous operation. The batch operation may employ a single tank reactor, and the aqueous calcium sulfide slurry, aqueous calcium hydrosulfide solution, and aqueous sodium sulfide solution may be added to the sulfuric acid-containing waste liquid, but it is preferable to add the sulfuric acid-containing waste liquid to the aqueous calcium sulfide slurry, aqueous calcium hydrosulfide solution, or aqueous sodium sulfide solution. Semi-continuous operation may be the alternate production of hydrogen sulfide gas using several batch-operated tank reactors. The continuous operation can adopt a cascade multi-groove series reactor, and can also adopt other continuous reactors.
Detailed description of the preferred embodiment
Example one
Adding 250ml of water into a 500ml four-mouth glass flask, adding 45.2g (containing 75% of CaS by mass, 33.9g of 100% of CaS and 0.470mol) of powdery calcium sulfide roasted body (prepared by thermal reduction of calcium sulfate) into the flask at 20-50 ℃ while stirring, pulping for 0.5H to prepare a water slurry, and slowly dropwise adding 60ml (by-product generated when toluene is sulfonated, chlorinated, nitrated and diluted in sulfuric acid to prepare 2-nitro-4-methyl-5-chlorobenzenesulfonic acid) of sulfuric acid-containing waste liquid (the total acidity is 8.1mol/L, according to H, the proportion is H2SO4Reduced by 0.486mol), the escaped hydrogen sulfide gas is absorbed by 500ml of 2.0mol/L sodium hydroxide aqueous solution, and the H is measured and absorbed together2S is more than 0.400 mol. Calculated as calcium sulfide, H2The yield of S is more than 85.1%. Based on the total acid amount, H2The yield of S is more than 82.3%. The residual liquid after the hydrogen sulfide gas is escaped is filtered to obtain about 220g of wet filter cake and about 74g of crude calcium sulfate. The filtrate contains water-soluble calcium arylsulfonate, and can be treated by wastewater containing sodium sulfate to recover calcium sulfate and recover by-product sodium arylsulfonate from the filtrate.
Example two
250ml of water is added into a 500ml four-neck glass flask, 53.9g (40.4 g of CaS with 100 percent folding and 0.560mol) of the calcium sulfide roasted body in the example I is added into the flask at the temperature of 20-50 ℃ under stirring, and the mixture is pulped for 0.5hIntroducing 0.620mol of hydrogen sulfide gas at 20-40 ℃, filtering, and removing insoluble substances to obtain Ca (SH) -containing2210ml of the aqueous solution [ molar content 2.24mol/L, 100% by volume]Ca(SH)20.470mol]. The insoluble matter was washed with 250ml of water in several portions containing Ca (SH)2The washing water is used for preparing calcium sulfide water slurry in the next batch. Mixing the above Ca (SH)2The aqueous solution was placed in a 500ml four-necked glass flask, and 60ml of the sulfuric acid-containing waste liquid (total acidity 8.1mol/L, in terms of H) described in example I was slowly dropped at 20 → 70 ℃2SO4Reduced by 0.486mol), the escaped hydrogen sulfide gas is absorbed by 1000ml of 2.0mol/L sodium hydroxide aqueous solution, and the H is measured and absorbed together2More than 0.840 mol. According to Ca (SH)2Meter, H2The yield of S is more than 89.3%. Based on the total acid amount, H2The yield of S is above 86.4%. The residual liquid after the hydrogen sulfide gas escape is filtered and washed to obtain about 200g of wet filter cake, and about 63g (about 0.46mol) of calcium sulfate with quite high purity.
EXAMPLE III
The formulation of example two was followed, but the calcium hydrosulfide aqueous solution was slowly added to the sulfuric acid-containing waste liquor and the co-absorption of H was determined2S is more than 0.820 mol. According to Ca (SH)2Meter, H2The yield of S is more than 87.2%. Based on the total acid amount, H2The yield of S is above 84.3%.
Example four
According to example one, 160ml (total acidity 3.04mol/L, as H) of sulfuric acid-containing waste liquid was used instead of sulfuric acid-containing waste liquid (by-produced in the reaction of acetanilide with chlorosulfonic acid to produce p-acetamidobenzenesulfonyl chloride)2SO4Reduced by 0.486 mol). Measured co-absorption of H2S is more than 0.395 mol. Calculated as calcium sulfide, H2The yield of S is above 84.0%. Based on the total acid amount, H2The yield of S is more than 81.2%. The residual liquid after the hydrogen sulfide gas is escaped is filtered to obtain about 170g of wet filter cake and 56g of crude calcium sulfate. The filtrate contains calcium chloride and calcium p-acetamidobenzenesulfonate, and can be treated by waste water containing water-soluble sulfate to recover calcium sulfate.
EXAMPLE five
According to the second embodiment of the present invention,however, the sulfuric acid-containing waste liquid used was changed to 81ml (total acidity of 6.00mol/L, as H, of a by-product in the preparation of monosodium 2-aminobenzene-1, 4-disulfonate by sulfonation of m-aminobenzenesulfonic acid with fuming sulfuric acid, dilution with water, salting out with sodium chloride) of a sulfuric acid-containing waste liquid2SO4Reduced by 0.486 mol). Measured co-absorption of H2And S is more than 0.850 mol. According to Ca (SH)2Meter, H2The yield of S is more than 90.4%. Based on the total acid amount, H2The yield of S is more than 87.4%. The residual liquid after the hydrogen sulfide gas escape is filtered and washed to obtain about 200g of wet filter cake, and about 63g (about 0.46mol) of calcium sulfate with quite high purity.
EXAMPLE six
According to example two, the sulfuric acid-containing waste liquid used was changed to 97.2, which is a mixture of a plurality of sulfuric acid-containing waste liquids (by-produced in the synthesis of organic chemical products and intermediates by chemical reaction)ml (total acidity 5.00mol/L, as H)2SO4Reduced by 0.486 mol). Measured absorption H2S is more than 0.820 mol. According to Ca (SH)2Meter, H2The yield of S is more than 87.2%. Based on the total acid amount, H2The yield of S is above 84.3%. The residual liquid after the hydrogen sulfide gas escape is filtered and washed to obtain about 190g of wet filter cake containing 61g (about 0.45mol) of calcium sulfate with quite high purity. The filtrate can be further treated to recover calcium sulfate and other metal compounds.
EXAMPLE seven
53.9g (40.0 g of 100% CaS, 0.560mol) of the calcined calcium sulfide described in example I was placed in a 600ml glass beaker, and 250ml of a sodium sulfate-containing waste liquid (containing SO) by-produced in the production of disodium 4, 4 '-dinitrostilbene-2, 2' -disulfonate by oxidation and salting-out of 2-methyl-5-nitrobenzenesulfonic acid) was used＝2.58g-ion/L, reduced SO4 ＝0.645g-ion) at 20-70 ℃, filtering to obtain 210ml of sodium sulfide-containing aqueous solution (containing S)＝2.24g-ion/L, Z S＝0.470g-ion) and the filter cake is washed several times with 250ml of water, and the sulphide containing wash water is used for the next batch of leaching of the calcium sulphide. The washed crude calcium sulfate can be used for thermal reduction to prepare a calcium sulfide roasted body. The aqueous sodium sulfide solution was placed in a 500ml four-neck glass flaskIn the method, 63ml of the sulfuric acid-containing waste liquid (total acidity of 8.1mol/L, as H) described in the first example is slowly added dropwise at 20-70 deg.C2SO4Reduced by 0.513mol), the escaped hydrogen sulfide gas is absorbed by 500ml of 2.0mol/L sodium hydroxide aqueous solution, and the H is measured and absorbed together2S is more than 0.400mol, based on S＝Meter, H2The yield of S is more than 85.1%. Based on the total acid amount, H2The yield of S is more than 77.9%. The sodium sulfate-containing waste liquid after the hydrogen sulfide gas is escaped can be used for leaching the calcium sulfide roasting body in the next batch.
Example eight
Into a 500ml four-necked glass flask, 210ml of the aqueous sodium sulfide solution (containing S) described in example seven was charged＝2.24g-ion/L, Z S＝0.470 g-ion)), 102.0ml (total acidity of 5.00mol/L, as H) of the mixture of the sulfuric acid-containing waste liquids of example VI was slowly added dropwise at 20-70 deg.C2SO4Reduced by 0.510mol), was determined to co-absorb H2S is more than 0.400mol, based on S＝The yield is over 85.1 percent. The yield is over 78.4 percent based on the total acid.
Claims (8)
1. A method for producing hydrogen sulfide gas by using byproduct sulfuric acid-containing waste liquid and calcium hydrosulfide aqueous solution as starting materials comprises the following steps:
a. the sulfuric acid-containing waste liquid reacts with the calcium hydrosulfide water solution to generate hydrogen sulfide gas,
b. a part of the generated hydrogen sulfide gas is used for further processing to prepare other chemical products, the other part of the generated hydrogen sulfide gas is used for reacting with calcium sulfide water slurry prepared by pulping calcium sulfide calcinator with water, calcium sulfide is converted into calcium hydrosulfide, insoluble impurities are removed by filtration to obtain calcium hydrosulfide aqueous solution, the calcium hydrosulfide aqueous solution is used for the step a,
c. filtering the residual calcium sulfate water slurry after the hydrogen sulfide gas escapes from the step a to obtain a calcium sulfate wet filter cake,
d. the calcium sulfide roasted body used in the step b is prepared by carrying out thermal reduction on various cheap calcium sulfates,
the method is mainly characterized in that: the sulfuric acid-containing waste liquid used in the step a is a byproduct aqueous solution containing sulfuric acid and harmful organic matters in the production process of preparing organic chemical products and intermediate products through chemical reaction; the sulfuric acid-containing waste liquid is used independently, or a plurality of sulfuric acid-containing waste liquids are collected and mixed for reuse; the total acidity of various sulfuric acid-containing waste liquids is different, the total acidity calculated by H2SO4 is 0.40-11.0 mol/L,
in the preparation of aqueous calcium hydrosulfide solutions, CaS is reacted with H2The mol ratio of S is 1: 1.05-1.30, the temperature is 20-70 ℃, the operation pressure is 0.09-0.15 Mpa, and Ca (SH) is contained in the prepared calcium hydrosulfide aqueous solution2The molar content of (b) is 0.70mol/L to 4.20mol/L,
the sulfuric acid-containing waste liquid and the calcium hydrosulfide aqueous solution are subjected to liquid phase reaction to generate hydrogen sulfide gas, and the main conditions are as follows: in the waste liquor containing sulfuric acid2SO4The mole number of the total acid converted and Ca (SH) in the calcium hydrosulfide aqueous solution2The molar ratio of (A) to (B) is 1: 0.90-1.25, the temperature is 20-100 ℃, and the operating pressure is 0.08-0.30 MPa.
2. The method of claim 1, wherein: the sulfuric acid-containing waste liquid of claim 1, which is obtained from the following production process:
the sulfuric acid-containing waste liquid which is a byproduct in the preparation of 2-nitro-4-methyl-5-chlorobenzene sulfonic acid by sulfonating, chlorinating and nitrifying toluene in sulfuric acid,
or the sulfuric acid-containing waste liquid which is a byproduct in the preparation of 2-aminobenzene-1, 4-disulfonic acid monosodium salt by sulfonating m-aminobenzene sulfonic acid with fuming sulfuric acid, diluting with water and salting out with sodium chloride.
3. The method of claim 1, wherein: when the sulfuric acid-containing waste liquid contains organic sulfonic acid, organic carboxylic acid or hydrochloric acid, the waste liquid containing soluble sulfate is added into the residual liquid containing calcium sulfate after hydrogen sulfide gas is generated or the residual liquid after calcium sulfate is filtered out, so that calcium sulfonate, calcium carboxylate or calcium chloride in the waste liquid is converted into water-insoluble calcium sulfate, and the calcium sulfate is recovered.
4. The method of claim 1, wherein: the generated hydrogen sulfide gas is output through a pipeline and then is prepared into liquid hydrogen sulfide by a freezing and pressurizing liquefaction method.
5. The method of claim 1, wherein: the generated hydrogen sulfide gas is not liquefied and is directly used for or after passing through a buffer gas tank, is further processed into other chemicalproducts, including elemental sulfur, sodium sulfide, sodium hydrosulfide, ammonium sulfide, ammonium hydrosulfide, thiourea, methyl mercaptan, ethanethiol, dimethyl sulfide and dimethyl sulfoxide.
6. The method of claim 1, wherein: the various cheap calcium sulfates refer to the calcium sulfate which is a byproduct in the processing of the phosphate rock, the calcium sulfate which is a byproduct in the production process of synthesizing organic chemical products and intermediate products, various natural gypsums, or the calcium sulfate wet filter cake which is a byproduct in the step c in the method of claim 1.
7. The method of claim 1, wherein: when the calcium sulfide roasted body is prepared by carrying out thermal reduction on the calcium sulfate wet filter cake by-produced in the step c in the method of claim 1, mixing the calcium sulfate wet filter cake with coal powder, extruding the mixture into a hollow small cylinder, a solid small cylinder or a small ball, dehydrating the mixture at 100-200 ℃, and preparing the calcium sulfide roasted body by using a thermal reduction method.
8. The method of claim 1, wherein: the method of claim 1, wherein the calcium sulfate wet filter cake produced in step c is dehydrated at 100-200 ℃ to produce industrial gypsum.
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| CN103274369A (en) * | 2013-05-20 | 2013-09-04 | 包头市红天宇稀土磁材有限公司 | Circulating method for preparing concentrated sulfuric acid and solid product from dilute sulfuric acid |
| CN108040479B (en) * | 2015-04-03 | 2021-08-03 | 乔治亚州立大学研究基金会股份有限公司 | Hydrogen sulfide precursors and conjugates thereof |
| CN107324288B (en) * | 2017-07-05 | 2020-04-28 | 海若斯（北京）能源环保科技有限公司 | Comprehensive treatment and recycling process for acidic waste gypsum |
| CN108946681A (en) * | 2018-07-03 | 2018-12-07 | 贵州大学 | A kind of technique preparing wear-resisting silicon nitride ceramic material coproduction acid |
| CN110980655A (en) * | 2019-12-11 | 2020-04-10 | 西南科技大学 | Method for recovering sulfur from byproduct gypsum of sulfur-containing wastewater |
| CN114684842B (en) * | 2022-04-29 | 2022-12-02 | 山西铁峰化工有限公司 | Method for preparing sodium hydrosulfide and co-producing calcium sulfate |
| CN114684793A (en) * | 2022-05-20 | 2022-07-01 | 黔南民族师范学院 | Method for preparing elemental sulfur from titanium gypsum, titanium white waste acid and yellow phosphorus tail gas |
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