CN101973914B - Method for preparing salt-free 2-amino-1,5-naphthalenedisulfonic acid - Google Patents
Method for preparing salt-free 2-amino-1,5-naphthalenedisulfonic acid Download PDFInfo
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- CN101973914B CN101973914B CN201010527898XA CN201010527898A CN101973914B CN 101973914 B CN101973914 B CN 101973914B CN 201010527898X A CN201010527898X A CN 201010527898XA CN 201010527898 A CN201010527898 A CN 201010527898A CN 101973914 B CN101973914 B CN 101973914B
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Abstract
The invention discloses a method for preparing salt-free 2-amino-1,5-naphthalenedisulfonic acid, which comprises the following steps: (1) performing a sulfonation reaction; (2) refining sulfonation solution; (3) performing acid eduction; (4) decreasing and maintaining temperature; (5) centrifuging; (6) refining acid filtrate; and (7) recovering sulphuric acid tail gas and SO3 gas. Based on the technical scheme of the invention, the method for preparing salt-free 2-amino-1,5-naphthalenedisulfonic acid is suitable for industrial production, requires low sulfonation reaction temperature and mild reaction conditions, causes fewer byproducts, realizes high conversion rate and high selectivity, lowers labor intensity, allows the acid filtrate and harmful gas to be recycled and relieves environment pollution.
Description
Technical field
The invention belongs to the preparation method field of industrial chemicals, specifically relate to a kind of method for preparing salt-free Sulpho Tobias Acid, it take oleum and TOBIAS ACID 97MIN.& 98MIN. is raw material, adopts the operation technological process of recycled containing acidleach liquid, and serialization prepares salt-free Sulpho Tobias Acid.
Background technology
Salt-free Sulpho Tobias Acid can be used as the intermediate of composite reactive dyestuff, sensitive materials and organic dye.And reactive dyestuffs, sensitive materials and organic dye are used widely at textile industry, plate-making industry, dyestuffs industries, and Application Areas is in further expansion, therefore, also in continuous increase, there is wide market outlook and development space as the demand of the salt-free Sulpho Tobias Acid of intermediate.
The producer of domestic production at present mostly produces the salt Sulpho Tobias Acid is arranged, and produce the producer of salt-free Sulpho Tobias Acid seldom, and technique is all immature, and quality product is general, and energy consumption is large, and cost is higher, produces a large amount of waste water, and environment is caused to very large pollution.
Summary of the invention
For overcoming the defect on above-mentioned prior art; the invention provides a kind of method for preparing salt-free Sulpho Tobias Acid; the whole preparation process serialization of the method, mass-producing, be suitable for suitability for industrialized production, and the sulfonation reaction temperature is lower; the reaction conditions gentleness; by product is few, and transformation efficiency and selectivity are high, and labour intensity is low; produce containing the acid solution body and obtained recycled, alleviated the pollution to environment.
The present invention realizes that the above-mentioned purpose technical scheme is, a kind of method for preparing salt-free Sulpho Tobias Acid, and the method comprises the following steps:
(1) sulfonation reaction step: TOBIAS ACID 97MIN.& 98MIN. and oleum be by weight 10: 1～1: 10 at 5 ℃～55 ℃, under carry out sulfonation reaction, generate the sulfonated liquid containing salt-free Sulpho Tobias Acid;
(2) sulfonated liquid purification step: the sulfonated liquid walked in employing carries out refining with adsorbents through one or more levels absorption pillar and obtains refining sulfonated liquid;
(3) acid out step: at-15 ℃～70 ℃, utilize the acidleach liquid TOBIAS ACID 97MIN.& 98MIN. complete with unreacted in refining sulfonated liquid that contain of 300g/L～550g/L to proceed to react, make salt-free Sulpho Tobias Acid from containing acidleach liquid, separating out separation simultaneously;
(4) cooling maintains step: after cooling maintains in tank the mixing acid analysis of material liquid temp of upper step is reduced to-20 ℃～30 ℃, keep 1～4 hour, make the complete TOBIAS ACID 97MIN.& 98MIN. of unreacted in mixing acid analysis of material liquid carry out complete reaction, make salt-free Sulpho Tobias Acid from fully separating out containing acidleach liquid simultaneously;
(5) centrifugation step: cooling is maintained to the qualified and mixing acid analysis of material liquid that fully separate out of rear reaction and put into whizzer and carry out centrifugation; Obtain the salt-free Sulpho Tobias Acid of finished product in whizzer, whizzer bottom filtrate is sent into containing the acidleach liquid storage tank;
(6) containing acidleach liquid purification step: by upper step send into containing the acidleach liquid storage tank containing acidleach liquid, carry out refining with adsorbents through one or more levels absorption pillar, refine containing acidleach liquid, again send into the acid out tank and reuse after overregulating concentration;
(7) sulfuric acid tail gas and SO
3gas recovery step: the SO that dissociates and during by sulfonation reaction
3the sulfuric acid tail gas that gas and whizzer volatilize when centrifugal and SO
3after gas is introduced exhaust gas recovery system by induced draft fan, after absorbing with circulated sprinkling water, form acid solution, this acid solution can be used for regulating shop fixtures in the acid out tank and, containing the concentration of acidleach liquid, also can deliver to the TOBIAS ACID 97MIN.& 98MIN. workshop and recycle; Forming acid solution after absorbing is lower concentration.
Described sulfonation reaction step refers to that TOBIAS ACID 97MIN.& 98MIN. and oleum carry out sulfonation reaction according to a certain percentage at a certain temperature, generates the sulfonated liquid containing salt-free Sulpho Tobias Acid;
Oleum mass concentration in described sulfonation reaction step is (with SO
3meter) be 20%～65%, preferably 20%～35%; The weight ratio of oleum and TOBIAS ACID 97MIN.& 98MIN. is 10: 1～1: 10, preferably 5: 1～1: 5; The temperature of sulfonation reaction is 5 ℃～55 ℃, and preferably 15 ℃～35 ℃, sulfonation reaction is carried out under vacuum, and vacuum is formed by induced draft fan air inducing, and it is not very high that vacuum tightness requires, and purpose is to extract the SO that dissociates out
3gas gets final product; The time of sulfonation reaction is 1～5 hour.
Described sulfonated liquid purification step refers to and adopts sulfonated liquid to be made with extra care through one or more levels absorption pillar; The absorption pillar can be primary, secondary, tertiary or multi-level; The filler of absorption pillar be in cascade ring, Raschig ring, screen waviness, perforated plate corrugated, gac, porcelain ball any one or several combine arbitrarily; Wherein the particle diameter of gac, porcelain ball is 50 orders～350 orders.
Described acid out step refers at a certain temperature, certain densityly containing the acidleach liquid TOBIAS ACID 97MIN.& 98MIN. complete with unreacted in refining sulfonated liquid, proceeds to react, and makes salt-free Sulpho Tobias Acid separate out separation from contain acidleach liquid simultaneously; Form mixing acid analysis of material liquid; The preferred temperature of acid out is-15 ℃ ,-10 ℃ ,-5 ℃, 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ wherein a kind of, the acid solution formed after reclaiming with soft water or sulfuric acid tail gas containing the concentration of acidleach liquid is regulated, and after regulating, its preferred mass concentration is wherein a kind of of 300g/L, 350g/L, 400g/L, 450g/L, 500g/L, 550g/L; The weight ratio containing acidleach liquid total amount and refining sulfonated liquid regulated in the acid out tank is 10: 0.5～0.5: 10, preferably 5: 0.5～0.5: 5; In the acid out tank, containing acidleach liquid, come from containing acidleach liquid purification step; The acid out feed liquid refers to by salt-free Sulpho Tobias Acid crystalline particle, water, the formed mixed liquor of sulfuric acid.
Described cooling maintains step and refers to and maintain the acid out feed temperature of tank by putting into cooling, after being reduced to a certain degree, keep certain hour, make certain densityly containing the complete TOBIAS ACID 97MIN.& 98MIN. of unreacted in acidleach liquid and acid out feed liquid, to carry out complete reaction, make salt-free TOBIAS ACID 97MIN.& 98MIN. fully separate out from mother liquor simultaneously; The preferred value that temperature reduces is-20 ℃ ,-15 ℃ ,-10 ℃ ,-5 ℃, 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃ wherein a kind of; Preferably 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours wherein a kind of hold time.
Described centrifugation step refers to that acid out feed liquid that cooling is maintained to the qualified and abundant separation of rear reaction maintains tank from cooling and puts into whizzer and carry out centrifugation; Obtain the salt-free Sulpho Tobias Acid of finished product in whizzer, after artificial discharging, send into packaging process, mix rear pack warehouse-in; After centrifugal, containing acidleach liquid, send into containing acidleach liquid refining step.
Described containing acidleach liquid purification step refer to centrifugal out containing acidleach liquid, carry out refining with adsorbents through one or more levels absorption pillar, refine again send into the acid out tank and reclaim the acid solution formed and regulate concentration with soft water or sulfuric acid tail gas containing acidleach liquid after, recycling; The absorption pillar can be one-level, secondary or multistage; The filler of absorption pillar be in cascade ring, Raschig ring, screen waviness, perforated plate corrugated, gac, porcelain ball any one or several combine arbitrarily; Wherein the particle diameter of gac, porcelain ball is 50 orders～350 orders.
Described sulfuric acid tail gas and SO
3the SO that dissociates and when the gas recovery step refers to sulfonation reaction
3the sulfuric acid tail gas that gas and whizzer volatilize when centrifugal and SO
3after gas is introduced exhaust gas recovery system by induced draft fan, in one or more levels absorption pillar, after absorbing with circulated sprinkling water, form acid solution, this acid solution can be used for regulating shop fixtures in the acid out tank and, containing the concentration of acidleach liquid, also can deliver to the TOBIAS ACID 97MIN.& 98MIN. workshop and recycle; After the gas of unabsorbed extremely trace is up to standard, by the chimney high altitude discharge; The absorption pillar can be one-level, secondary or multistage; The filler of absorption pillar be in cascade ring, Raschig ring, screen waviness, perforated plate corrugated, gac, porcelain ball any one or several combine arbitrarily; Wherein the particle diameter of gac, porcelain ball is 50 orders～350 orders.
It is raw material that oleum and TOBIAS ACID 97MIN.& 98MIN. are take in the present invention, successively, acid out refining through sulfonation reaction, sulfonated liquid, cooling maintain, centrifugal, refining containing acidleach liquid, sulfuric acid tail gas and SO
3gas recovery, whole preparation process serialization, mass-producing, be suitable for suitability for industrialized production; The sulfonation reaction temperature of preparation process is lower, the reaction conditions gentleness, and by product is few, and transformation efficiency and selectivity are high, and labour intensity is low, and the acidleach liquid that contains of generation has obtained recycle, has alleviated the pollution to environment; The content of prepared salt-free Sulpho Tobias Acid is higher than 98.5% (HPLC), and the yield of suitability for industrialized production is higher than 93.5%.Therefore, economic benefit of the present invention and social benefit be highly significant all, especially environment protection, promotion sustained economic development is produced to far-reaching influence, has broad application prospects.
The accompanying drawing explanation
Fig. 1 is the process flow sheet that the present invention prepares salt-free Sulpho Tobias Acid;
Fig. 2 relates to the refining part process flow sheet of sulfonated liquid;
Fig. 3 relates to containing the refining part process flow sheet of acidleach liquid;
Fig. 4 relates to sulfuric acid tail gas and SO
3the part process flow sheet of gas recovery.
Embodiment
Below in conjunction with accompanying drawing 1, Fig. 2, Fig. 3 and Fig. 4, the technical process of the salt-free Sulpho Tobias Acid of preparation of technical solution of the present invention is described below respectively:
1. sulfonation reaction operation:
The technical process of sulfonation reaction is, by volume pump, a certain amount of oleum sent in sulphonation kettle, opens and stirs, and opens induced draft fan simultaneously, makes in sulphonation kettle to form vacuum, the SO dissociating
3gas is introduced exhaust gas recovery system; The logical refrigerated water cooling of sulphonation kettle chuck, when temperature drops to a certain degree, by the sulphonation kettle charging opening, in proportion a certain amount of TOBIAS ACID 97MIN.& 98MIN. is slowly added in sulphonation kettle, carry out sulfonation reaction, maintain certain hour after adding, produce the sulfonated liquid containing salt-free Sulpho Tobias Acid.
In sulfonation reaction, the weight ratio of oleum and TOBIAS ACID 97MIN.& 98MIN. is for being 10: 1～1: 10, preferably 5: 1～1: 5, and for example 5: 1,5: 2,4: 2,1: 2,1: 3,1: 4,3: 5; Oleum concentration is (with SO
3meter) be 20%～65%, preferably 20%～35%; The temperature of sulfonation reaction is 5 ℃～35 ℃, such as 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ etc., a temperature value in preferably 15 ℃～35 ℃, usually can control temperature of reaction not higher than 35 ℃, the reaction times of material in whole reactor is 1～5 hour, whole reaction is carried out under vacuum, and it is not very high that vacuum tightness requires, and purpose is to extract the SO that dissociates out
3gas gets final product.
2. sulfonated liquid refining step:
The main task of sulfonated liquid refining step is impurity and the pigment removed in sulfonated liquid, obtains quality refining sulfonated liquid preferably.Treating process is for carrying out refining with adsorbents by sulfonated liquid through filling Packed one or more levels absorption pillar with impeller pump; The absorption pillar can be one-level, secondary or multistage; The filler of absorption pillar be in cascade ring, Raschig ring, screen waviness, perforated plate corrugated, gac, porcelain ball any one or several combine arbitrarily; Wherein the particle diameter of gac, porcelain ball is 50 orders～350 orders.
3. acid out operation:
The acid out operation refers at a certain temperature, certain densityly containing the acidleach liquid TOBIAS ACID 97MIN.& 98MIN. complete with unreacted in refining sulfonated liquid, proceeds to react, and makes salt-free Sulpho Tobias Acid separate out separation from contain acidleach liquid simultaneously;
The technological process of acid out operation is: at first, with impeller pump, send in proportion shop fixtures in the acid out tank to what refine after centrifugal containing acidleach liquid, after arriving certain liquid level, open and stir, after 5～10 minutes, sampling analysis is containing the acidity value of sour female filtrate; If do not reach required value, to reclaim with soft water or sulfuric acid tail gas the acid solution formed and regulated, making its acidity value after adjusting is wherein a kind of of 300g/L, 350g/L, 400g/L, 450g/L, 500g/L, 550g/L; Then the sulfonated liquid refined of certainweight, slowly put into the acid out tank, to control the temperature of material in the acid out tank be-15 ℃ ,-10 ℃ ,-5 ℃, 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ wherein a kind of to logical refrigerated water simultaneously; The weight ratio containing acidleach liquid total amount and refining sulfonated liquid regulated in the acid out tank is 10: 0.5～0.5: 10, preferably 5: 0.5～0.5: 5; After certain hour, get the filtrate sample analysis of acid out feed liquid, during amino value≤25g/L, the acid out feed liquid is put into to cooling and maintain tank.
The acid out feed liquid refers to by salt-free Sulpho Tobias Acid crystalline particle, water, the formed mixed liquor of sulfuric acid.
The filtrate of acid out feed liquid refers to that the acid out feed liquid is at the liquid obtained after qualitative filter paper filters in filter flask.
4. cooling maintains operation:
The technical process that cooling maintains operation is: the acid out feed liquid is put into after cooling maintains tank, coil pipe leads to chilled brine, continue to reduce the temperature of acid out feed liquid, after temperature is reduced to a certain degree, maintain certain hour, make the complete TOBIAS ACID 97MIN.& 98MIN. of unreacted in the acid out feed liquid carry out complete reaction, make salt-free Sulpho Tobias Acid from fully separating out containing acidleach liquid simultaneously; The temperature of acid out feed liquid is reduced to-20 ℃ ,-15 ℃ ,-10 ℃ ,-5 ℃, 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃ wherein a kind of; Maintain 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours wherein a kind of; Get the filtrate sample analysis of acid out feed liquid, during amino value≤15g/L, the acid out feed liquid is put into to the whizzer centrifugal discharge.
The filtrate of acid out feed liquid refers to that the acid out feed liquid is at the liquid obtained after qualitative filter paper filters in filter flask.
5. rotary process:
The process of rotary process is: open cooling and maintains the pot bottom valve, cooling is maintained to the qualified and acid out feed liquid that fully separate out of rear reaction and by pipeline, put into whizzer, after discharging, close dispensing valve; Start whizzer and carry out centrifugation, cover the whizzer upper cover simultaneously, cover sulfuric acid tail gas and SO in conducting
3gas removes the induced draft fan passage, then starts induced draft fan; After certain hour, get the salt-free Sulpho Tobias Acid sample analysis in whizzer, after content reaches requirement, artificial discharging, send into packaging process, mixes rear pack warehouse-in; The centrifugal bottom acidleach liquid that contains is out collected containing acidleach liquid storage tank by pipeline.
6. containing acidleach liquid refining step:
Containing acidleach liquid refining step: containing in acidleach liquid storage tank centrifugal out contain acidleach liquid, carry out refining with adsorbents through one or more levels absorption pillar under the effect of impeller pump, refine containing acidleach liquid, again send into vacant acid out tank, with soft water or sulfuric acid tail gas and SO
3gas is absorbed by water the acid solution formed to carry out reusing after concentration adjustment concentration; The absorption pillar can be primary, secondary, tertiary or multi-level; The filler of absorption pillar be in cascade ring, Raschig ring, screen waviness, perforated plate corrugated, gac, porcelain ball any one or several combine arbitrarily; Wherein the particle diameter of gac, porcelain ball is 50 orders～350 orders.
7. sulfuric acid tail gas and SO
3the gas recovery operation:
Sulfuric acid tail gas and SO
3the technical process of gas recovery: the SO that dissociates and during by sulfonation reaction
3the sulfuric acid tail gas that gas and whizzer volatilize when centrifugal and SO
3after gas is introduced exhaust gas recovery system by induced draft fan, in one or more levels absorption pillar, after absorbing with circulated sprinkling water, form acid solution, this acid solution can be used for regulating shop fixtures in the acid out tank and, containing the concentration of acidleach liquid, also can deliver to the TOBIAS ACID 97MIN.& 98MIN. workshop and recycle; After the gas of unabsorbed extremely trace is up to standard, by the chimney high altitude discharge; The absorption pillar can be one-level, secondary or multistage; The filler of absorption pillar be in cascade ring, Raschig ring, screen waviness, perforated plate corrugated, gac, porcelain ball any one or several combine arbitrarily; Wherein the particle diameter of gac, porcelain ball is 50 orders～350 orders.
Relating to sulfonated liquid makes with extra care, makes with extra care and sulfuric acid tail gas and SO containing acidleach liquid
3the concrete operations mode of the part technique of gas recovery is:
Sulfonated liquid is made with extra care the concrete operations mode, referring to Fig. 2, open the sulphonation kettle bottom valve, open acid out tank material inlet valve, start crude product sulfonated liquid transferpump, adjust flux, to 2000L/h, makes sulfonated liquid successively through filling Packed primary, secondary, tertiary or multi-level absorption pillar, after impurity absorption in sulfonated liquid is refining, send in the acid out tank; In the acid out tank, be covered with in advance regulated concentration containing acidleach liquid; After sulfonated liquid has been beaten, stop the sulfonated liquid transferpump, close sulphonation kettle bottom valve and acid out tank material inlet valve.Detect at any time the refining sulfonated liquid through the absorption pillar, if refining sulfonated liquid darkens, in the filtrate of refining sulfonated liquid, amino value increases, and will check that in the absorption pillar, whether filler is saturated, if reach capacity state, change in time filler.
The filtrate of refining sulfonated liquid refers to the liquid after typing filter paper suction filtration for refining sulfonated liquid; The filler state that reaches capacity, filling adsorption has been described too much impurity, can not recur adsorption, must be changed.
Filtrate is made with extra care the concrete operations mode, referring to Fig. 3, open containing acidleach liquid storage tank bottom valve, opening the acid out tank advances containing the acidleach fluid valve, start containing acidleach liquid transferpump, adjust flux, to 2000L/h, makes containing acidleach liquid successively through filling Packed primary, secondary, tertiary or multi-level absorption pillar, after making with extra care containing the impurity absorption in acidleach liquid, send in vacant acid out tank; Detect the acidity value that contains acidleach liquid in the acid out tank, if not up to standard, reclaim with soft water or sulfuric acid tail gas the acid solution formed and regulated, making its acidity value after adjusting is 400g/L; After arriving specified location containing acidleach liquid in the acid out tank, stop, containing acidleach liquid transferpump, closing containing acidleach liquid storage tank bottom valve and acid out tank to advance containing the acidleach fluid valve.Detect at any time through the absorption pillar containing acidleach liquid color and amino value, if darken containing acidleach liquid, amino value increases, and will check that in the absorption pillar, whether filler saturated, if reach capacity state, change in time filler.
Containing acidleach liquid darken, amino value increases and refers to containing being contrasted after the absorption of acidleach liquid with before adsorbing; The filler state that reaches capacity, filling adsorption has been described too much impurity, can not recur adsorption, must be changed.
Sulfuric acid tail gas and SO
3at first the concrete operations mode of the part technique of gas recovery, referring to Fig. 4,, with transferpump, squeeze into 2000Kg soft water in circulation groove standby, 100Kg soft water is squeezed in liquid seal can, and liquid level need seal from the exhaust pipe end opening that gets off of absorption pillar top, plays the effect of fluid-tight, close spray water recycle pump disacidify and analyse tank or TOBIAS ACID 97MIN.& 98MIN. workshop bypass valve, open spray water recycle pump terminal valve, start the spray water recycle pump, make soft water enter the spray water sparger from absorption pillar top, form atomize, start induced draft fan, allow SO from sulphonation kettle
3gas and from sulfuric acid tail gas and the SO3 gas at whizzer top, under the effect of induced draft fan, from one-level absorption pillar bottom sides, enter, through packing layer, after being absorbed by the spray water from one-level absorption pillar top, become acid solution and flow into circulation groove, do not have absorbed tail gas to continue to adsorb the pillar roof deck out from one-level under the effect at induced draft fan, enter secondary, three grades or multistage absorption pillar continue to be absorbed by the spray water from top, until 99.99% tail gas is absorbed, only have denier to reach the gas of emission standard, enter atmosphere from the high altitude discharge chimney,
Detect at any time the acid strength in circulation groove, when acid solution can not absorb SO again
3or acid liquor temperature will change acid solution while raising in time, now, open spray water recycle pump disacidify and analyse tank or TOBIAS ACID 97MIN.& 98MIN. workshop bypass valve, close spray water recycle pump terminal valve; After in circulation groove, acid solution has been beaten, supplement in time soft water, in order to circulation next time, absorb and use.
Below, provide the embodiment of the reaction process that several technical solution of the present invention adopt:
Embodiment 1-sulfonation reaction:
Sickle formula agitator is housed to one, 2 opening for feeds, add 20% oleum 500 grams in five mouthfuls of flasks of condenser and hot resistance, now a charging opening is guided to suction opening with flexible pipe, another charging opening seals with cork, starts and stirs, and logical refrigerated water is cooling, when temperature drops to 10 ℃, slowly add 100 gram TOBIAS ACID 97MIN.& 98MIN., after adding, continue reaction 2.5 hours, stop stirring, reaction finishes.
Whole reaction unit is installed in stink cupboard, in case SO
3gas overflowing is hurted sb.'s feelings.
After reaction finishes, the filtrate analysis of getting sulfonated liquid, amino value is 28g/L, reacts qualified (amino value≤30g/L is qualified); The filtrate of sulfonated liquid refers to that sulfonated liquid is at the liquid obtained after qualitative filter paper filters in filter flask.
Embodiment 2-sulfonation reaction:
Sickle formula agitator is housed to one, 2 opening for feeds, add 25% oleum 400 grams in five mouthfuls of flasks of condenser and hot resistance, now a charging opening is guided to suction opening with flexible pipe, another charging opening seals with cork, starts and stirs, and logical refrigerated water is cooling, when temperature drops to 5 ℃, slowly add 200 gram TOBIAS ACID 97MIN.& 98MIN., after adding, continue reaction 2 hours, stop stirring, reaction finishes.
Whole reaction unit is installed in stink cupboard, in case SO
3gas overflowing is hurted sb.'s feelings.
After reaction finishes, the filtrate analysis of getting sulfonated liquid, amino value is 29g/L, reacts qualified (amino value≤30g/L is qualified).
Embodiment 3-sulfonation reaction:
Sickle formula agitator is housed to one, 2 opening for feeds, add 30% oleum 300 grams in five mouthfuls of flasks of condenser and hot resistance, now a charging opening is guided to suction opening with flexible pipe, another charging opening seals with cork, starts and stirs, and logical refrigerated water is cooling, when temperature drops to 5 ℃, slowly add 600 gram TOBIAS ACID 97MIN.& 98MIN., after adding, continue reaction 3.5 hours, stop stirring, reaction finishes.
Whole reaction unit is installed in stink cupboard, in case SO
3gas overflowing is hurted sb.'s feelings.
After reaction finishes, the filtrate analysis of getting sulfonated liquid, amino value is 31g/L, reacts qualified (amino value≤35g/L is qualified).
Embodiment 4-sulfonation reaction:
Sickle formula agitator is housed to one, 2 opening for feeds, add 35% oleum 500 grams in five mouthfuls of flasks of condenser and hot resistance, now a charging opening is guided to suction opening with flexible pipe, another charging opening seals with cork, starts and stirs, and logical refrigerated water is cooling, when temperature drops to 5 ℃, slowly add 200 gram TOBIAS ACID 97MIN.& 98MIN., after adding, continue reaction 2.5 hours, stop stirring, reaction finishes.
Whole reaction unit is installed in stink cupboard, in case SO
3gas overflowing is hurted sb.'s feelings.
After reaction finishes, the filtrate analysis of getting sulfonated liquid, amino value is 30g/L, reacts qualified (amino value≤35g/L is qualified).
Embodiment 5-acid out operation:
To one, sickle formula agitator is housed, 2 opening for feeds, in five mouthfuls of flasks of condenser and hot resistance, add refine containing acidleach liquid 500 grams, now a charging opening is guided to suction opening with flexible pipe, another charging opening seals with cork, start and stir, add 100 gram soft water, stir after 10 minutes, sampling analysis, acidity value containing acidleach liquid is 500g/L, then, the logical refrigerated water of flask inner coil pipe is cooling, temperature is controlled at 25 ℃ of left and right, the sulfonated liquid that slowly adds 200 grams to refine, after adding, continue stirring reaction 3 hours, form the acid out feed liquid, stop stirring, acid out finishes.
So-called acid out feed liquid refers to by salt-free Sulpho Tobias Acid crystalline particle, water, sulfuric acid and the formed mixed liquor of micro-TOBIAS ACID 97MIN.& 98MIN..
Whole reaction unit is installed in stink cupboard, in case micro-SO
3gas overflowing is hurted sb.'s feelings.
Get the filtrate sample analysis of acid out feed liquid, when amino value is 24g/L, react qualified (amino value≤25g/L is qualified).
The filtrate of acid out feed liquid refers to that the acid out feed liquid is at the liquid obtained after qualitative filter paper filters in filter flask.
Embodiment 6-acid out operation:
To one, sickle formula agitator is housed, 2 opening for feeds, in five mouthfuls of flasks of condenser and hot resistance, add refine containing acidleach liquid 500 grams, now a charging opening is guided to suction opening with flexible pipe, another charging opening seals with cork, start and stir, add 400 gram soft water, stir after 10 minutes, sampling analysis, acidity value containing acidleach liquid is 450g/L, then, the logical refrigerated water of flask inner coil pipe is cooling, temperature is controlled at 35 ℃ of left and right, the sulfonated liquid that slowly adds 300 grams to refine, after adding, continue stirring reaction 2.5 hours, form the acid out feed liquid, stop stirring, acid out finishes.
So-called acid out feed liquid refers to by salt-free Sulpho Tobias Acid crystalline particle, water, sulfuric acid and the formed mixed liquor of micro-TOBIAS ACID 97MIN.& 98MIN..
Whole reaction unit is installed in stink cupboard, in case micro-SO
3gas overflowing is hurted sb.'s feelings.
Get the filtrate sample analysis of acid out feed liquid, when amino value is 23.6g/L, react qualified (amino value≤25g/L is qualified).
The filtrate of acid out feed liquid refers to that the acid out feed liquid is at the liquid obtained after qualitative filter paper filters in filter flask.
Embodiment 7-acid out operation:
To one, sickle formula agitator is housed, 2 opening for feeds, in five mouthfuls of flasks of condenser and hot resistance, add refine containing acidleach liquid 600 grams, now a charging opening is guided to suction opening with flexible pipe, another charging opening seals with cork, start and stir, add 200 grams to reclaim acid solution, stir after 10 minutes, sampling analysis, acidity value containing acidleach liquid is 550g/L, then, the logical refrigerated water of flask inner coil pipe is cooling, temperature is controlled at 30 ℃ of left and right, the sulfonated liquid that slowly adds 300 grams to refine, after adding, continue stirring reaction 2 hours, form the acid out feed liquid, stop stirring, acid out finishes.
So-called acid out feed liquid refers to by salt-free Sulpho Tobias Acid crystalline particle, water, sulfuric acid and the formed mixed liquor of micro-TOBIAS ACID 97MIN.& 98MIN..
Whole reaction unit is installed in stink cupboard, in case micro-SO
3gas overflowing is hurted sb.'s feelings.
Get the filtrate sample analysis of acid out feed liquid, when amino value is 22g/L, react qualified (amino value≤25g/L is qualified).
The filtrate of acid out feed liquid refers to that the acid out feed liquid is at the liquid obtained after qualitative filter paper filters in filter flask.
Embodiment 8-acid out operation:
To one, sickle formula agitator is housed, 2 opening for feeds, in five mouthfuls of flasks of condenser and hot resistance, add refine containing acidleach liquid 200 grams, now a charging opening is guided to suction opening with flexible pipe, another charging opening seals with cork, start and stir, add 200 grams to reclaim acid solution, stir after 10 minutes, sampling analysis, acidity value containing acidleach liquid is 350g/L, then, the logical refrigerated water of flask inner coil pipe is cooling, temperature is controlled at 20 ℃ of left and right, the sulfonated liquid that slowly adds 400 grams to refine, after adding, continue stirring reaction 2 hours, form the acid out feed liquid, stop stirring, acid out finishes.
The acid out feed liquid refers to by salt-free Sulpho Tobias Acid crystalline particle, water, sulfuric acid and the formed mixed liquor of micro-TOBIAS ACID 97MIN.& 98MIN..
Whole reaction unit is installed in stink cupboard, in case micro-SO
3gas overflowing is hurted sb.'s feelings.
Get the filtrate sample analysis of acid out feed liquid, when amino value is 24.5g/L, react qualified (amino value≤25g/L is qualified).
The filtrate of acid out feed liquid refers to that the acid out feed liquid is at the liquid obtained after qualitative filter paper filters in filter flask
Embodiment 9-cooling maintains:
To one, sickle formula agitator is housed, 2 opening for feeds, add acid out feed liquid 500 grams in five mouthfuls of flasks of condenser and hot resistance, now a charging opening is guided to suction opening with flexible pipe, and another charging opening seals with cork, start and stir, logical refrigerated water is cooling, when temperature drops to 5 ℃, continues to maintain reaction 1.5 hours, stop stirring, cooling maintains end.
Whole reaction unit is installed in stink cupboard, in case micro-SO
3gas overflowing is hurted sb.'s feelings.
After reaction finishes, get the filtrate analysis of acid out feed liquid, amino value is 13g/L, reacts qualified (amino value≤15g/L is qualified).
The filtrate of acid out feed liquid refers to that the acid out feed liquid is at the liquid obtained after qualitative filter paper filters in filter flask.
Embodiment 10-cooling maintains:
To one, sickle formula agitator is housed, 2 opening for feeds, add acid out feed liquid 500 grams in five mouthfuls of flasks of condenser and hot resistance, now a charging opening is guided to suction opening with flexible pipe, and another charging opening seals with cork, start and stir, logical refrigerated water is cooling, when temperature drops to 0 ℃, continues to maintain reaction 1 hour, stop stirring, cooling maintains end.
Whole reaction unit is installed in stink cupboard, in case micro-SO
3gas overflowing is hurted sb.'s feelings.
After reaction finishes, get the filtrate analysis of acid out feed liquid, amino value is 14g/L, reacts qualified (amino value≤15g/L is qualified).
The filtrate of acid out feed liquid refers to that the acid out feed liquid is at the liquid obtained after qualitative filter paper filters in filter flask.
Embodiment 11-cooling maintains:
To one, sickle formula agitator is housed, 2 opening for feeds, add acid out feed liquid 500 grams in five mouthfuls of flasks of condenser and hot resistance, now a charging opening is guided to suction opening with flexible pipe, and another charging opening seals with cork, start and stir, logical refrigerated water is cooling, when temperature drops to-5 ℃, continues to maintain reaction 2 hours, stop stirring, cooling maintains end.
Whole reaction unit is installed in stink cupboard, in case micro-SO
3gas overflowing is hurted sb.'s feelings.
After reaction finishes, get the filtrate analysis of acid out feed liquid, amino value is 14.5g/L, reacts qualified (amino value≤15g/L is qualified).
The filtrate of acid out feed liquid refers to that the acid out feed liquid is at the liquid obtained after qualitative filter paper filters in filter flask.
Embodiment 12-cooling maintains:
To one, sickle formula agitator is housed, 2 opening for feeds, add acid out feed liquid 500 grams in five mouthfuls of flasks of condenser and hot resistance, now a charging opening is guided to suction opening with flexible pipe, and another charging opening seals with soft, start and stir, logical refrigerated water is cooling, when temperature drops to 15 ℃, continues to maintain reaction 3 hours, stop stirring, cooling maintains end.
Whole reaction unit is installed in stink cupboard, in case micro-SO
3gas overflowing is hurted sb.'s feelings.
After reaction finishes, get the filtrate analysis of acid out feed liquid, amino value is 12g/L, reacts qualified (amino value≤15g/L is qualified).
The filtrate of acid out feed liquid refers to that the acid out feed liquid is at the liquid obtained after qualitative filter paper filters in filter flask.
Technique scheme has only embodied the optimal technical scheme of technical solution of the present invention, and those skilled in the art have all embodied principle of the present invention to some changes that wherein some part may be made, within belonging to protection scope of the present invention.
Claims (8)
1. a method for preparing salt-free Sulpho Tobias Acid, is characterized in that, the method comprises the following steps:
(1) sulfonation reaction step: TOBIAS ACID 97MIN.& 98MIN. and oleum by weight be 10:1～1:10 under 5 ℃～55 ℃, carry out sulfonation reaction, the time of reaction is 1～5 hour, generate to contain the sulfonated liquid of salt-free Sulpho Tobias Acid;
(2) sulfonated liquid purification step: the sulfonated liquid walked in employing carries out refining with adsorbents through one or more levels absorption pillar and obtains refining sulfonated liquid;
(3) acid out step: at-15 ℃～70 ℃, utilize the acidleach liquid TOBIAS ACID 97MIN.& 98MIN. complete with unreacted in refining sulfonated liquid that contain of 300g/L～550g/L to proceed to react, make salt-free Sulpho Tobias Acid from containing acidleach liquid, separating out separation simultaneously;
(4) cooling maintains step: after cooling maintains in tank the mixing acid analysis of material liquid temp of upper step is reduced to-20 ℃～30 ℃, keep 1～4 hour, make the complete TOBIAS ACID 97MIN.& 98MIN. of unreacted in mixing acid analysis of material liquid carry out complete reaction, make salt-free Sulpho Tobias Acid from fully separating out containing acidleach liquid simultaneously;
(5) centrifugation step: cooling is maintained to the qualified and mixing acid analysis of material liquid that fully separate out of rear reaction and put into whizzer and carry out centrifugation; Obtain the salt-free Sulpho Tobias Acid of finished product in whizzer, whizzer bottom filtrate is sent into containing the acidleach liquid storage tank;
(6) containing acidleach liquid purification step: by upper step send into containing the acidleach liquid storage tank containing acidleach liquid, carry out refining with adsorbents through one or more levels absorption pillar, refine containing acidleach liquid, again send into the acid out tank and reuse after overregulating concentration;
(7) sulfuric acid tail gas and SO
3gas recovery step: the SO that dissociates and during by sulfonation reaction
3the sulfuric acid tail gas that gas and whizzer volatilize when centrifugal and SO
3after gas is introduced exhaust gas recovery system by induced draft fan, after absorbing with circulated sprinkling water, form acid solution, this acid solution can be used for regulating shop fixtures in the acid out tank and, containing the concentration of acidleach liquid, also can deliver to the TOBIAS ACID 97MIN.& 98MIN. workshop and recycle; Forming acid solution after absorbing is lower concentration.
2. the method for the salt-free Sulpho Tobias Acid of preparation according to claim 1, is characterized in that the main raw material in described sulfonation reaction step is oleum and TOBIAS ACID 97MIN.& 98MIN..
3. the method for the salt-free Sulpho Tobias Acid of preparation according to claim 1, it is characterized in that, the mass concentration of described oleum is 20%～65%, the weight ratio 5:1 of oleum and TOBIAS ACID 97MIN.& 98MIN.～1:5, the temperature of sulfonation reaction is 5 ℃～55 ℃, and the time of sulfonation reaction is 1～5 hour.
4. the method for the salt-free Sulpho Tobias Acid of preparation according to claim 1, is characterized in that, the sulfonated liquid in described sulfonated liquid purification step is to reach refining purpose by the impurity in one or more levels absorption pillar Filtration Adsorption sulfonated liquid; The absorption pillar can be one or more levels; The filler of absorption pillar be in cascade ring, Raschig ring, screen waviness, perforated plate corrugated, gac, porcelain ball any one or several combine arbitrarily; The particle diameter of use therein gac or porcelain ball is 50 orders～350 orders.
5. the method for the salt-free Sulpho Tobias Acid of preparation according to claim 1, it is characterized in that, the acid out temperature in described acid out step is a kind of in-15 ℃ ,-10 ℃ ,-5 ℃, 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃; Be to reclaim with soft water or sulfuric acid tail gas the acid solution formed to regulate and form containing acidleach liquid, regulate rear its mass concentration and be wherein a kind of of 300g/L, 350g/L, 400g/L, 450g/L, 500g/L, 550g/L; The weight ratio containing acidleach liquid total amount and refining sulfonated liquid regulated in the acid out tank is 10:0.5～0.5:10; In the acid out tank, containing acidleach liquid, come from containing acidleach liquid purification step; The acid out feed liquid refers to by salt-free Sulpho Tobias Acid crystalline particle, water, the formed mixed liquor of sulfuric acid.
6. the method for the salt-free Sulpho Tobias Acid of preparation according to claim 1, it is characterized in that, described cooling maintains step and refers to that acid out feed liquid in the acid out tank is put into to cooling maintains tank, after temperature is reduced to a certain degree, keep certain hour, make the complete TOBIAS ACID 97MIN.& 98MIN. of unreacted in the acid out feed liquid carry out complete reaction, make salt-free Sulpho Tobias Acid from fully separating out containing acidleach liquid simultaneously; The temperature reduced is preferably-20 ℃ ,-15 ℃ ,-10 ℃ ,-5 ℃, 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃ wherein a kind of; The time kept is 1～4 hour.
7. the method for the salt-free Sulpho Tobias Acid of preparation according to claim 1, it is characterized in that, described containing acidleach liquid purification step be whizzer centrifugal out contain acidleach liquid, carry out refining with adsorbents through one or more levels absorption pillar, refine containing acidleach liquid, again, after sending into the acid out tank and reclaiming the acid solution formed and regulated with soft water or sulfuric acid tail gas, as the shop fixtures mother liquor, reuse; The absorption pillar can be one or more levels; The filler of absorption pillar be in cascade ring, Raschig ring, screen waviness, perforated plate corrugated, gac, porcelain ball any one or several combine arbitrarily; The particle diameter of gac wherein, porcelain ball is 50 orders～350 orders.
8. the method for the salt-free Sulpho Tobias Acid of preparation according to claim 1, is characterized in that, described sulfuric acid tail gas and SO
3the gas recovery step is the SO that dissociates and during by sulfonation reaction
3the sulfuric acid tail gas that gas and whizzer volatilize when centrifugal and SO
3after gas is introduced exhaust gas recovery system by induced draft fan, in the absorption pillar with after circulated sprinkling water spray-absorption, forming acid solution; After the gas of unabsorbed extremely trace is up to standard, by the chimney high altitude discharge; Reclaim acid solution and can be used for regulating the concentration of the interior shop fixtures of acid out tank containing acidleach liquid, also can deliver to the TOBIAS ACID 97MIN.& 98MIN. workshop and recycle; The absorption pillar can be one or more levels; The filler of absorption pillar be in cascade ring, Raschig ring, screen waviness, perforated plate corrugated, gac, porcelain ball any one or several combine arbitrarily; Wherein the particle diameter of gac, porcelain ball is 50 orders～350 orders.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010527898XA CN101973914B (en) | 2010-11-02 | 2010-11-02 | Method for preparing salt-free 2-amino-1,5-naphthalenedisulfonic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010527898XA CN101973914B (en) | 2010-11-02 | 2010-11-02 | Method for preparing salt-free 2-amino-1,5-naphthalenedisulfonic acid |
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| CN101973914A CN101973914A (en) | 2011-02-16 |
| CN101973914B true CN101973914B (en) | 2013-11-13 |
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| CN103992249B (en) * | 2014-05-29 | 2016-01-20 | 山西翔宇化工有限公司 | A kind of preparation method of TOBIAS ACID 97MIN.& 98MIN. sodium salt |
| CN105084600B (en) * | 2015-08-28 | 2017-11-24 | 浙江奇彩环境科技股份有限公司 | A kind of method and its application of efficient process salt-containing organic wastewater |
| CN109876758A (en) * | 2019-04-02 | 2019-06-14 | 天津市科德化工有限公司 | Sulpho Tobias Acid sulfonating reaction kettle |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4199529A (en) * | 1977-10-03 | 1980-04-22 | Ciba-Geigy Ag | Process for the production of amino-I-acid |
| CN1070396A (en) * | 1991-09-12 | 1993-03-31 | 拜尔公司 | 2-naphthylamines-1, the separation method of 5-disulfonic acid |
| CN1280123A (en) * | 1999-07-13 | 2001-01-17 | 天津市环境保护科学研究院 | Method for preparing J acid (7-amino-4-hydroxy-2-naphthalonesulfonic acid) |
-
2010
- 2010-11-02 CN CN201010527898XA patent/CN101973914B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4199529A (en) * | 1977-10-03 | 1980-04-22 | Ciba-Geigy Ag | Process for the production of amino-I-acid |
| CN1070396A (en) * | 1991-09-12 | 1993-03-31 | 拜尔公司 | 2-naphthylamines-1, the separation method of 5-disulfonic acid |
| CN1280123A (en) * | 1999-07-13 | 2001-01-17 | 天津市环境保护科学研究院 | Method for preparing J acid (7-amino-4-hydroxy-2-naphthalonesulfonic acid) |
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