阅读说明：本技术 一种溴氨酸合成新工艺 (Novel process for synthesizing bromamine acid ) 是由 时娇娇 李超 于 2021-01-12 设计创作，主要内容包括：本发明涉及一种溴氨酸合成新工艺,包括：步骤一,加入1-氨基蒽醌作为原料后加入邻二氯苯并滴入氯磺酸以进行磺化反应,到达磺化反应终点后,加入硫酸加入溴化钠和溴酸钠进行溴化反应,到达溴化反应终点后在分层装置中进行溴化分层；步骤二,当中控模块判定所述溴化分层完成时,将溴化料放入第二反应器内并加入液碱进行中和反应得到溴氨酸滤饼；步骤三,当中控模块判定水不溶物析出完全时,将溴氨酸滤饼放入第三反应器内并加入活性炭进行活性炭热精反应；步骤四,将进行活性炭热精反应后的溴氨酸滤饼依次经过盐析、压滤和干燥后得到溴氨酸；从而能够解决溴氨酸内含有水不溶物的问题,进而有效提高了溴氨酸成品的质量和收率。(The invention relates to a novel process for synthesizing bromamine acid, which comprises the following steps: adding 1-aminoanthraquinone as a raw material, adding o-dichlorobenzene and dripping chlorosulfonic acid to carry out sulfonation reaction, adding sulfuric acid, adding sodium bromide and sodium bromate to carry out bromination reaction after the end point of the sulfonation reaction is reached, and carrying out bromination layering in a layering device after the end point of the bromination reaction is reached; step two, when the central control module judges that the bromination layering is finished, bromide materials are placed into a second reactor and added with liquid alkali for neutralization reaction to obtain a bromamine acid filter cake; step three, when the central control module judges that the water-insoluble substances are completely separated out, putting the bromamine acid filter cake into a third reactor and adding active carbon to carry out active carbon thermal refining reaction; step four, sequentially salting out, filter-pressing and drying the bromamine acid filter cake subjected to the activated carbon thermal refining reaction to obtain bromamine acid; thereby solving the problem that the bromamine acid contains water-insoluble substances, and further effectively improving the quality and the yield of the finished product of the bromamine acid.)

1. A novel technology for synthesizing bromamine acid is characterized by comprising the following steps:

adding 1-aminoanthraquinone serving as a raw material into a first reactor through a first feed port, adding o-dichlorobenzene into the first reactor through a second feed port, dripping chlorosulfonic acid through a dripping pipe orifice to perform sulfonation reaction, adding sulfuric acid into the first reactor through a third feed port after the end point of the sulfonation reaction is reached, adding sodium bromide and sodium bromate into the first reactor through a fourth feed port to perform bromination reaction, performing bromination layering in a layering device after the end point of the bromination reaction is reached to obtain a brominated material and o-dichlorobenzene, and distilling and recovering the o-dichlorobenzene;

step two, when the central control module judges that the bromination layering is finished, the brominated materials are placed into a second reactor, liquid caustic soda is added through a fifth feeding hole for neutralization reaction so as to separate out water insoluble substances in the brominated materials, and after the neutralization reaction reaches the end point, the brominated materials are sequentially cooled and filtered to obtain bromamine acid filter cakes;

step three, when the central control module judges that the water-insoluble substance is completely separated out, putting the bromamine acid filter cake into a third reactor, adding activated carbon through a sixth feeding hole to perform an activated carbon thermal refining reaction so as to adsorb the water-insoluble substance in the bromamine acid filter cake and recover the used waste activated carbon;

step four, sequentially salting out, filter-pressing and drying the bromamine acid filter cake subjected to the activated carbon thermal refining reaction to obtain bromamine acid;

when the bromination reaction end point is reached, putting a part of product after the bromination reaction into the layering device for bromination layering, controlling a density detector by a central control module to detect the density of the o-dichlorobenzene after bromination layering, and comparing the actual measured density with the parameters in a preset o-dichlorobenzene density matrix rho a0 to determine the amount of sulfuric acid required to be added again;

when the o-dichlorobenzene is obtained by bromination layering in the layering device, the central control module controls the density detector to detect the density of the o-dichlorobenzene in the layering device again and compares the detected density detected again with a preset o-dichlorobenzene standard density to judge whether bromination layering is finished or not; when the central control module judges that the bromination layering is not finished, adding water into the layering device to carry out secondary layering on the o-dichlorobenzene so as to obtain a brominated layering material and new o-dichlorobenzene, and distilling and recycling the new o-dichlorobenzene;

before adding the liquid caustic soda, the central control module controls a quality detector to detect the quality of the brominated material and compares the measured actual quality with parameters in a preset vulcanized material quality matrix mx0 to determine the amount of the added liquid caustic soda;

when the liquid caustic soda is added, the central control module controls a pH value detector to detect the pH value of the brominated material and compares the detected actual pH value with the preset pH value of the brominated material to judge whether the water-insoluble substance is completely separated out;

before the activated carbon thermal refining reaction is carried out, the central control module controls a concentration detector to detect the concentration of the bromamine acid filter cake and compares the measured actual concentration with parameters in a preset concentration matrix eta 0 to determine the amount of added activated carbon;

the central control module is provided with a preset pH value P0 of a brominated material, a preset pH value difference matrix delta P0 and a liquid caustic soda addition matrix mb 0; for the preset pH value difference matrix DeltaP 0, setting DeltaP 0 (DeltaP 1, DeltaP 2 and DeltaP 3), wherein DeltaP 1 represents a first difference of the preset pH value, DeltaP 2 represents a second difference of the preset pH value, DeltaP 3 represents a third difference of the preset pH value, and DeltaP 1 is less than DeltaP 2 and less than DeltaP 3; setting mb0 (mb 1, mb2, mb3 and mb 4) for the liquid caustic soda supplementation matrix mb0, wherein mb1 represents a first liquid caustic soda supplementation, mb2 represents a second liquid caustic supplementation, mb3 represents a third liquid caustic supplementation, mb4 represents a fourth liquid caustic supplementation, and mb1 < mb2 < mb3 < mb 4;

when the liquid caustic soda is added, the actual pH value measured by the pH value detector is marked as P, and when the detection is finished, the central control module compares the actual pH value P with the preset pH value P0 of the brominated material:

if P is more than or equal to P0, the central control module judges that the water-insoluble substance is completely separated out;

if P is less than P0, the central control module judges that the water-insoluble substance is not completely separated out;

when the central control module judges that the precipitation of the water-insoluble substances is incomplete, the central control module calculates the pH value difference value delta P, sets delta P = P0-P, compares the pH value difference value delta P with parameters in a preset pH value difference matrix delta P0 when the calculation is completed,

if delta P is less than delta P1, the central control module sets the amount of the liquid caustic soda added into the fifth feed inlet again to be mb 1;

if the delta P is more than or equal to delta P1 and less than delta P2, the amount of the liquid alkali added into the fifth feeding hole is set to be mb2 by the central control module;

if the delta P is more than or equal to delta P2 and less than delta P3, the amount of the liquid alkali added into the fifth feeding hole is set to be mb3 by the central control module;

if the delta P is not less than the delta P3, the central control module sets the liquid alkali adding amount of the fifth feeding hole to be mb4 again.

2. The novel process for synthesizing bromamine acid according to claim 1, wherein the central control module is further provided with a preset concentration matrix eta 0 and an activated carbon addition matrix mt0; setting eta 0 (eta 1, eta 2, eta 3) for the preset concentration matrix eta 0, wherein eta 1 represents a preset first concentration, eta 2 represents a preset second concentration, eta 3 represents a preset third concentration, and eta 1 is more than eta 2 and less than eta 3; for the activated carbon addition matrix mt0, mt0 (mt 1, mt2, mt3 and mt 4) is set, wherein mt1 represents a first activated carbon addition, mt2 represents a second activated carbon addition, mt3 represents a third activated carbon addition, mt4 represents a fourth activated carbon addition, and mt1 < mt2 < mt3 < mt 4;

in the third step, before the activated carbon thermal refining reaction is performed, the actual concentration measured by the concentration detector is recorded as eta, and when the detection is completed, the central control module compares the actual concentration eta with parameters in a preset concentration matrix eta 0:

if eta is less than eta 1, the central control module sets the amount of the activated carbon added into the sixth feeding hole as mt 1;

if eta 1 is not more than eta and is less than eta 2, the central control module sets the amount of the activated carbon added into the sixth feed inlet as mt 2;

if eta 2 is not less than eta < eta 3, the central control module sets the amount of the activated carbon added into the sixth feed inlet as mt 3;

if eta is larger than or equal to eta 3, the central control module sets the amount of the activated carbon added into the sixth feed inlet as mt 4;

and after the central control module controls the sixth feeding hole to add mti-amount of activated carbon into the third reactor, the central control module controls the concentration detector to detect the concentration of the bromamine acid filter cake again.

3. The novel process for synthesizing bromamine acid according to claim 2, wherein in the third step, when the central control module controls the concentration detector to detect the concentration of the bromamine acid filter cake again, the secondary detection concentration measured by the concentration detector is recorded as η s, meanwhile, the central control module is provided with a preset standard concentration η s0, η s0 is set to be less than η 1, and when the detection and the presetting are completed, the central control module compares the secondary detection concentration η s with the preset standard concentration η s 0:

if eta s is less than or equal to eta s0, the central control module judges that the hot refining reaction of the activated carbon is finished;

if eta s is more than eta s0, the central control module judges that the heat refining reaction of the activated carbon is not completed and controls a sixth feeding port to add the activated carbon again to adsorb the water-insoluble substances in the bromamine acid filter cake.

4. The novel process for synthesizing bromamine acid according to claim 3, wherein said central control module is further provided with a preset concentration difference matrix Δ η 0, and Δ η 0 (Δ η 1,. DELTA.η 2,. DELTA.η 3) is set, wherein Δ η 1 represents a first difference of preset concentration, Δ η 2 represents a second difference of preset concentration, Δ η 3 represents a third difference of preset concentration, and Δ η 1 <. DELTA.η 2 <. DELTA.η 3;

when eta s is larger than eta s0, the central control module calculates the concentration difference delta eta, and the calculation formula is as follows:

△η=（ηs-ηs0）×δ；

wherein δ represents a concentration difference coefficient, and δ = η s/η s0 is set;

when the calculation is finished, the central control module compares the concentration difference value delta eta with the parameters in the preset concentration difference value matrix delta eta 0,

if Δ η <. eta.1, the central control module sets the amount of activated carbon added again at the sixth feed inlet to mh1, setting mh1= mt1 × 0.1;

if the delta eta 1 is less than or equal to the delta eta < delta eta 2, the central control module sets the amount of the activated carbon added again at the sixth feeding hole to mh2, and mh2= mt2 × 0.2 is set;

if the delta eta 2 is less than or equal to the delta eta < delta eta 3, the central control module sets the amount of the activated carbon added again at the sixth feeding hole to mh3, and mh3= mt3 × 0.3 is set;

if the delta eta is not less than or equal to the delta eta 3, the central control module sets the amount of the activated carbon added again at the sixth feeding hole to mh4, and mh4= mt4 × 0.4 is set;

wherein mti represents the ith addition of activated carbon, and i =1,2,3,4 is set.

5. The novel process for synthesizing bromamine acid according to claim 1, wherein the central control module is further provided with a preset o-dichlorobenzene density matrix p a0 and a sulfuric acid addition matrix ml 0; setting rho a0 (rho a1, rho a2 and rho a 3) for the preset ortho-dichlorobenzene density matrix rho a0, wherein rho a1 represents a preset ortho-dichlorobenzene first density, rho a2 represents a preset ortho-dichlorobenzene second density, rho a3 represents a preset ortho-dichlorobenzene third density, and rho a1 & lt rho a2 & lt rho a 3; for the sulfuric acid addition matrix ml0, ml0 (ml 1, ml2, ml3, ml 4) is set, wherein ml1 represents a first addition of sulfuric acid, ml2 represents a second addition of sulfuric acid, ml3 represents a third addition of sulfuric acid, ml4 represents a fourth addition of sulfuric acid, ml1 < ml2 < ml3 < ml 4;

in the first step, when a part of the powder is put into the layering device for bromination layering, the actual density measured by the density detector is recorded as ρ, and when the detection is finished, the central control module compares the actual density ρ with the parameters in a preset o-dichlorobenzene density matrix ρ a 0:

if rho is more than rho a1, the central control module sets the amount of sulfuric acid added into the third feed port again to be ml 1;

if rho is not less than rho 1 and is more than rho a2, the central control module sets the amount of sulfuric acid added into the third feed port to be ml2 again;

if rho is not less than rho 2 and is more than rho a3, the central control module sets the amount of sulfuric acid added into the third feed port to be ml3 again;

if the rho is larger than or equal to rho a3, setting the amount of sulfuric acid added into the third feed port again to be ml4 by the central control module;

and the central control module controls the third feeding port to add the sulfuric acid with the mli amount again, and then the bromination reaction is continued in the first reactor, wherein i =1,2,3 and 4 are set.

6. The new technology for synthesizing bromamine acid according to claim 5, wherein when the central control module controls the third feed port to add mli amount of sulfuric acid again and perform bromination layering in the layering device to obtain o-dichlorobenzene, i =1,2,3,4 is set, the density detected again by the density detector is recorded as ρ s, meanwhile, the central control module is provided with a preset o-dichlorobenzene standard density ρ 0, ρ 0 > ρ a4, and when the detection and the setting are completed, the central control module compares the density ρ s detected again with the preset o-dichlorobenzene standard density ρ 0:

if rho s is larger than or equal to rho 0, the central control module judges that the bromination layering is finished;

and if rho s is less than rho 0, the central control module judges that the bromination layering is not finished.

7. The novel process for synthesizing bromamine acid according to claim 6, wherein the central control module is further provided with a preset density difference matrix Δ ρ s0 and a water addition amount matrix mj 0; for the preset density difference matrix Δ ρ s0, Δ ρ s0 (Δ ρ s1, Δ ρ s2, Δ ρ s 3) is set, where Δ ρ s1 represents a preset first density difference, Δ ρ s2 represents a preset second density difference, Δ ρ s3 represents a preset third density difference, and Δ ρ s1 < [ Δ ρ s2 < [ Δ ρ s3 ]; setting mj0 (mj 1, mj2, mj3 and mj 4) for the water adding amount matrix mj0, wherein mj1 represents a first water adding amount, mj2 represents a second water adding amount, mj3 represents a third water adding amount, mj4 represents a fourth water adding amount, and mj1 < mj2 < mj3 < mj 4;

when the central control module judges that the bromination layering is not finished, the central control module calculates a density difference value delta rho s, and the water adding amount is calculated as follows:

△ρs=（ρ0-ρs）×σ；

where σ denotes a density difference coefficient, and σ = ρ 0/ρ s is set;

when the calculation is finished, the central control module compares the density difference value delta rho s with the parameters in the preset density difference value matrix delta rho s0,

if the delta rho s is less than the delta rho s1, the central control module sets the water adding amount in the layered device to mj 1;

if the delta rho s1 is less than or equal to the delta rho s2, the central control module sets the water adding amount in the layering device to mj 2;

if the delta rho s2 is less than or equal to the delta rho s3, the central control module sets the water adding amount in the layering device to mj 3;

if the delta rho s is not less than the delta rho s3, the central control module sets the water adding amount in the layered device to mj 4.

8. The new process for synthesizing bromamine acid according to claim 1, wherein the central control module is further provided with a preset sulfide mass matrix mx0, and mx0 (mx 1, mx2, mx 3) is set, wherein mx1 represents a preset sulfide first mass, mx2 represents a preset sulfide second mass, mx3 represents a preset sulfide third mass, mx1 < mx2 < mx 3;

in the second step, before the liquid caustic soda is added, the actual mass measured by the mass detector is recorded as mx, and when the mass detector finishes detection, the central control module compares the actual mass mx with parameters in a preset vulcanizing material mass matrix mx 0:

if mx is less than mx1, the central control module determines that the amount of the liquid alkali added at the fifth feed inlet is my1, and sets my1=10 xmb 1;

if mx1 is not less than mx and is less than mx2, the central control module judges that the amount of the liquid alkali added into the fifth feed port is my2, and my2=20 xmb 2 is set;

if mx2 is not less than mx and is less than mx3, the central control module judges that the amount of the liquid alkali added into the fifth feeding hole is my3, and my3=30 xmb 3 is set;

if mx is larger than or equal to mx3, the central control module judges that the amount of the liquid caustic soda added to the fifth feed port is my4, and my4=10 xmb 4 is set;

wherein myi represents the i th supplementary amount of the liquid caustic soda, and i =1,2,3,4 is set.

9. The novel process for synthesizing bromamine acid according to claim 4, wherein when the central control module determines that the thermal refining reaction of the activated carbon is not completed, the amount of the activated carbon is not added, and the amount of the filter cloth is directly adjusted in the subsequent filter pressing process to separate out water-insoluble substances.

Technical Field

The invention relates to the field of organic synthesis, in particular to a novel process for synthesizing bromamine acid.

Background

Bromamine acid, chemical name is 1-amino-4-bromo-2-sulfonic acid anthraquinone, which is an important dye intermediate, and is mainly used for manufacturing acid anthraquinone type dyes such as weak acid brilliant blue GAW, weak acid brilliant blue R, reactive brilliant blue M-BR, brilliant blue KN-R, brilliant blue K3R, brilliant blue KGR and the like.

In the synthesis process of bromamine acid, 1-aminoanthraquinone which is used as an important intermediate undergoes sulfonation reaction and bromination reaction to finally generate bromamine acid. Chinese patent publication No. 104086430a discloses a method for synthesizing 1-aminoanthraquinone, in which anthraquinone and nitric acid are subjected to an insufficient nitration reaction in a solvent to obtain 1-nitroanthraquinone, and a 1-aminoanthraquinone mixture is obtained through a reduction reaction, because the reaction for producing 1-nitroanthraquinone is an exothermic reaction, the exothermic reaction easily causes an excessive reaction temperature to cause side reactions, which result in a large amount of by-products, and the purity of the product is affected by the production of the by-products, and the yield is reduced.

At present, some new processes for synthesizing bromamine acid are available, but insoluble substances are generated, the insoluble substances are side reactants generated in the reaction process of the new processes, and the substances cause difficulty in post-treatment and separation of the new processes and influence the quality and yield of bromamine acid finished products.

Disclosure of Invention

Therefore, the invention provides a novel process for synthesizing bromamine acid, which can effectively solve the technical problem of low quality and yield of bromamine acid finished products caused by water insoluble substances generated in the prior art.

In order to achieve the above object, the present invention provides a novel process for synthesizing bromamine acid, comprising:

adding 1-aminoanthraquinone serving as a raw material into a first reactor through a first feed port, adding o-dichlorobenzene into the first reactor through a second feed port, dripping chlorosulfonic acid through a dripping pipe orifice to perform sulfonation reaction, adding sulfuric acid into the first reactor through a third feed port after the end point of the sulfonation reaction is reached, adding sodium bromide and sodium bromate into the first reactor through a fourth feed port to perform bromination reaction, performing bromination layering in a layering device after the end point of the bromination reaction is reached to obtain a brominated material and o-dichlorobenzene, and distilling and recovering the o-dichlorobenzene;

step two, when the central control module judges that the bromination layering is finished, the brominated materials are placed into a second reactor, liquid caustic soda is added through a fifth feeding hole for neutralization reaction so as to separate out water insoluble substances in the brominated materials, and after the neutralization reaction reaches the end point, the brominated materials are sequentially cooled and filtered to obtain bromamine acid filter cakes;

step three, when the central control module judges that the water-insoluble substance is completely separated out, putting the bromamine acid filter cake into a third reactor, adding activated carbon through a sixth feeding hole to perform an activated carbon thermal refining reaction so as to adsorb the water-insoluble substance in the bromamine acid filter cake and recover the used waste activated carbon;

step four, sequentially salting out, filter-pressing and drying the bromamine acid filter cake subjected to the activated carbon thermal refining reaction to obtain bromamine acid;

when the bromination reaction end point is reached, putting a part of product after the bromination reaction into the layering device for bromination layering, controlling a density detector by a central control module to detect the density of the o-dichlorobenzene after bromination layering, and comparing the actual measured density with the parameters in a preset o-dichlorobenzene density matrix rho a0 to determine the amount of sulfuric acid required to be added again;

when the o-dichlorobenzene is obtained by bromination layering in the layering device, the central control module controls the density detector to detect the density of the o-dichlorobenzene in the layering device again and compares the detected density detected again with a preset o-dichlorobenzene standard density to judge whether bromination layering is finished or not; when the central control module judges that the bromination layering is not finished, adding water into the layering device to carry out secondary layering on the o-dichlorobenzene so as to obtain a brominated layering material and new o-dichlorobenzene, and distilling and recycling the new o-dichlorobenzene;

before adding the liquid caustic soda, the central control module controls a quality detector to detect the quality of the brominated material and compares the measured actual quality with parameters in a preset vulcanized material quality matrix mx0 to determine the amount of the added liquid caustic soda;

when the liquid caustic soda is added, the central control module controls a pH value detector to detect the pH value of the brominated material and compares the detected actual pH value with the preset pH value of the brominated material to judge whether the water-insoluble substance is completely separated out;

before the activated carbon thermal refining reaction is carried out, the central control module controls a concentration detector to detect the concentration of the bromamine acid filter cake and compares the measured actual concentration with parameters in a preset concentration matrix eta 0 to determine the amount of added activated carbon;

the central control module is provided with a preset pH value P0 of a brominated material, a preset pH value difference matrix delta P0 and a liquid caustic soda addition matrix mb 0; for the preset pH value difference matrix DeltaP 0, setting DeltaP 0 (DeltaP 1, DeltaP 2 and DeltaP 3), wherein DeltaP 1 represents a first difference of the preset pH value, DeltaP 2 represents a second difference of the preset pH value, DeltaP 3 represents a third difference of the preset pH value, and DeltaP 1 is less than DeltaP 2 and less than DeltaP 3; setting mb0 (mb 1, mb2, mb3 and mb 4) for the liquid caustic soda supplementation matrix mb0, wherein mb1 represents a first liquid caustic soda supplementation, mb2 represents a second liquid caustic supplementation, mb3 represents a third liquid caustic supplementation, mb4 represents a fourth liquid caustic supplementation, and mb1 < mb2 < mb3 < mb 4;

when the liquid caustic soda is added, the actual pH value measured by the pH value detector is marked as P, and when the detection is finished, the central control module compares the actual pH value P with the preset pH value P0 of the brominated material:

if P is more than or equal to P0, the central control module judges that the water-insoluble substance is completely separated out;

if P is less than P0, the central control module judges that the water-insoluble substance is not completely separated out;

when the central control module judges that the precipitation of the water-insoluble substances is incomplete, the central control module calculates the pH value difference value delta P, sets delta P = P0-P, compares the pH value difference value delta P with parameters in a preset pH value difference matrix delta P0 when the calculation is completed,

if delta P is less than delta P1, the central control module sets the amount of the liquid caustic soda added into the fifth feed inlet again to be mb 1;

if the delta P is more than or equal to delta P1 and less than delta P2, the amount of the liquid alkali added into the fifth feeding hole is set to be mb2 by the central control module;

if the delta P is more than or equal to delta P2 and less than delta P3, the amount of the liquid alkali added into the fifth feeding hole is set to be mb3 by the central control module;

if the delta P is not less than the delta P3, the central control module sets the liquid alkali adding amount of the fifth feeding hole to be mb4 again.

Further, the central control module is also provided with a preset concentration matrix eta 0 and an active carbon addition matrix mt0; setting eta 0 (eta 1, eta 2, eta 3) for the preset concentration matrix eta 0, wherein eta 1 represents a preset first concentration, eta 2 represents a preset second concentration, eta 3 represents a preset third concentration, and eta 1 is more than eta 2 and less than eta 3; for the activated carbon addition matrix mt0, mt0 (mt 1, mt2, mt3 and mt 4) is set, wherein mt1 represents a first activated carbon addition, mt2 represents a second activated carbon addition, mt3 represents a third activated carbon addition, mt4 represents a fourth activated carbon addition, and mt1 < mt2 < mt3 < mt 4;

in the third step, before the activated carbon thermal refining reaction is performed, the actual concentration measured by the concentration detector is recorded as eta, and when the detection is completed, the central control module compares the actual concentration eta with parameters in a preset concentration matrix eta 0:

if eta is less than eta 1, the central control module sets the amount of the activated carbon added into the sixth feeding hole as mt 1;

if eta 1 is not more than eta and is less than eta 2, the central control module sets the amount of the activated carbon added into the sixth feed inlet as mt 2;

if eta 2 is not less than eta < eta 3, the central control module sets the amount of the activated carbon added into the sixth feed inlet as mt 3;

if eta is larger than or equal to eta 3, the central control module sets the amount of the activated carbon added into the sixth feed inlet as mt 4;

and after the central control module controls the sixth feeding hole to add mti-amount of activated carbon into the third reactor, the central control module controls the concentration detector to detect the concentration of the bromamine acid filter cake again.

Further, in the third step, when the central control module controls the concentration detector to detect the concentration of the bromamine acid filter cake again, the secondary detection concentration measured by the concentration detector is recorded as η s, meanwhile, the central control module is provided with a preset standard concentration η s0, η s0 is set to be less than η 1, and when the detection and the presetting are completed, the central control module compares the secondary detection concentration η s with the preset standard concentration η s 0:

if eta s is less than or equal to eta s0, the central control module judges that the hot refining reaction of the activated carbon is finished;

if eta s is more than eta s0, the central control module judges that the heat refining reaction of the activated carbon is not completed and controls a sixth feeding port to add the activated carbon again to adsorb the water-insoluble substances in the bromamine acid filter cake.

Further, the central control module is further provided with a preset concentration difference matrix delta eta 0, and delta eta 0 (delta eta 1, delta eta 2 and delta eta 3) is set, wherein delta eta 1 represents a first difference of preset concentration, delta eta 2 represents a second difference of preset concentration, delta eta 3 represents a third difference of preset concentration, and delta eta 1 is less than delta eta 2 and less than delta eta 3;

when eta s is larger than eta s0, the central control module calculates the concentration difference delta eta, and the calculation formula is as follows:

△η=（ηs-ηs0）×δ；

wherein δ represents a concentration difference coefficient, and δ = η s/η s0 is set;

when the calculation is finished, the central control module compares the concentration difference value delta eta with the parameters in the preset concentration difference value matrix delta eta 0,

if Δ η <. eta.1, the central control module sets the amount of activated carbon added again at the sixth feed inlet to mh1, setting mh1= mt1 × 0.1;

if the delta eta 1 is less than or equal to the delta eta < delta eta 2, the central control module sets the amount of the activated carbon added again at the sixth feeding hole to mh2, and mh2= mt2 × 0.2 is set;

if the delta eta 2 is less than or equal to the delta eta < delta eta 3, the central control module sets the amount of the activated carbon added again at the sixth feeding hole to mh3, and mh3= mt3 × 0.3 is set;

if the delta eta is not less than or equal to the delta eta 3, the central control module sets the amount of the activated carbon added again at the sixth feeding hole to mh4, and mh4= mt4 × 0.4 is set;

wherein mti represents the ith addition of activated carbon, and i =1,2,3,4 is set.

Further, the central control module is also provided with a preset ortho-dichlorobenzene density matrix rho a0 and a sulfuric acid addition matrix ml 0; setting rho a0 (rho a1, rho a2 and rho a 3) for the preset ortho-dichlorobenzene density matrix rho a0, wherein rho a1 represents a preset ortho-dichlorobenzene first density, rho a2 represents a preset ortho-dichlorobenzene second density, rho a3 represents a preset ortho-dichlorobenzene third density, and rho a1 & lt rho a2 & lt rho a 3; for the sulfuric acid addition matrix ml0, ml0 (ml 1, ml2, ml3, ml 4) is set, wherein ml1 represents a first addition of sulfuric acid, ml2 represents a second addition of sulfuric acid, ml3 represents a third addition of sulfuric acid, ml4 represents a fourth addition of sulfuric acid, ml1 < ml2 < ml3 < ml 4;

in the first step, when a part of the powder is put into the layering device for bromination layering, the actual density measured by the density detector is recorded as ρ, and when the detection is finished, the central control module compares the actual density ρ with the parameters in a preset o-dichlorobenzene density matrix ρ a 0:

if rho is more than rho a1, the central control module sets the amount of sulfuric acid added into the third feed port again to be ml 1;

if rho is not less than rho 1 and is more than rho a2, the central control module sets the amount of sulfuric acid added into the third feed port to be ml2 again;

if rho is not less than rho 2 and is more than rho a3, the central control module sets the amount of sulfuric acid added into the third feed port to be ml3 again;

if the rho is larger than or equal to rho a3, setting the amount of sulfuric acid added into the third feed port again to be ml4 by the central control module;

and the central control module controls the third feeding port to add the sulfuric acid with the mli amount again, and then the bromination reaction is continued in the first reactor, wherein i =1,2,3 and 4 are set.

Further, when the central control module controls the third feed port to add mli amount of sulfuric acid again and perform bromination layering in the layering device to obtain the o-dichlorobenzene, i =1,2,3,4 is set, the density detected again by the density detector is recorded as ρ s, meanwhile, the central control module is provided with a preset o-dichlorobenzene standard density ρ 0, ρ 0 > ρ a4, and when the detection and the setting are completed, the central control module compares the density ρ s detected again with the preset o-dichlorobenzene standard density ρ 0:

if rho s is larger than or equal to rho 0, the central control module judges that the bromination layering is finished;

and if rho s is less than rho 0, the central control module judges that the bromination layering is not finished.

Further, the central control module is also provided with a preset density difference matrix delta rho 0 and a water adding quantity matrix mj 0; for the preset density difference matrix Δ ρ s0, Δ ρ s0 (Δ ρ s1, Δ ρ s2, Δ ρ s 3) is set, where Δ ρ s1 represents a preset first density difference, Δ ρ s2 represents a preset second density difference, Δ ρ s3 represents a preset third density difference, and Δ ρ s1 < [ Δ ρ s2 < [ Δ ρ s3 ]; setting mj0 (mj 1, mj2, mj3 and mj 4) for the water adding amount matrix mj0, wherein mj1 represents a first water adding amount, mj2 represents a second water adding amount, mj3 represents a third water adding amount, mj4 represents a fourth water adding amount, and mj1 < mj2 < mj3 < mj 4;

when the central control module judges that the bromination layering is not finished, the central control module calculates a density difference value delta rho s, and the water adding amount is calculated as follows:

△ρs=（ρ0-ρs）×σ；

where σ denotes a density difference coefficient, and σ = ρ 0/ρ s is set;

when the calculation is finished, the central control module compares the density difference value delta rho s with the parameters in the preset density difference value matrix delta rho s0,

if the delta rho s is less than the delta rho s1, the central control module sets the water adding amount in the layered device to mj 1;

if the delta rho s1 is less than or equal to the delta rho s2, the central control module sets the water adding amount in the layering device to mj 2;

if the delta rho s2 is less than or equal to the delta rho s3, the central control module sets the water adding amount in the layering device to mj 3;

if the delta rho s is not less than the delta rho s3, the central control module sets the water adding amount in the layered device to mj 4.

Further, the central control module is further provided with a preset vulcanizing material mass matrix mx0, and mx0 (mx 1, mx2, mx 3) is set, wherein mx1 represents a first preset vulcanizing material mass, mx2 represents a second preset vulcanizing material mass, mx3 represents a third preset vulcanizing material mass, and mx1 < mx2 < mx 3;

in the second step, before the liquid caustic soda is added, the actual mass measured by the mass detector is recorded as mx, and when the mass detector finishes detection, the central control module compares the actual mass mx with parameters in a preset vulcanizing material mass matrix mx 0:

if mx is less than mx1, the central control module determines that the amount of the liquid alkali added at the fifth feed inlet is my1, and sets my1=10 xmb 1;

if mx1 is not less than mx and is less than mx2, the central control module judges that the amount of the liquid alkali added into the fifth feed port is my2, and my2=20 xmb 2 is set;

if mx2 is not less than mx and is less than mx3, the central control module judges that the amount of the liquid alkali added into the fifth feeding hole is my3, and my3=30 xmb 3 is set;

if mx is larger than or equal to mx3, the central control module judges that the amount of the liquid caustic soda added to the fifth feed port is my4, and my4=10 xmb 4 is set;

wherein myi represents the i th supplementary amount of the liquid caustic soda, and i =1,2,3,4 is set.

Further, when the central control module judges that the thermal refining reaction of the activated carbon is not completed, the dosage of the activated carbon can be not added, and the dosage of the filter cloth is directly adjusted in the subsequent filter pressing process so as to separate out the water-insoluble substances.

Compared with the prior art, the method has the advantages that the actual density is compared with the parameters in the preset o-dichlorobenzene density matrix rho a0 to determine the amount of sulfuric acid required to be added again, the density detected again is compared with the preset o-dichlorobenzene standard density to judge whether bromination layering is completed, the actual quality is compared with the parameters in the preset sulfide mass matrix mx0 to determine the amount of liquid alkali to be added, the actual pH value is compared with the preset pH value of a bromide to judge whether the water-insoluble substance is completely separated out, the actual concentration is compared with the parameters in the preset concentration matrix eta 0 to determine the amount of the added active carbon, the pH value difference delta P is compared with the parameters in the preset pH value difference matrix delta P0 to determine the amount of the added liquid alkali again, so that the water-insoluble substance can be separated out by adding the liquid alkali and then is adsorbed by adding the active carbon, solves the problem that the bromamine acid contains water-insoluble substances, and further effectively improves the quality and yield of the finished bromamine acid product on the premise of ensuring the process stability.

Further, the method compares the actual mass mx with the parameters in the preset sulfide mass matrix mx0 to determine the amount of the added liquid caustic soda, so that the amount of the added liquid caustic soda can be accurately controlled, and the quality and yield of the finished product of the bromamine acid are effectively improved on the premise of ensuring the process stability.

Furthermore, the amount of the added active carbon is determined by comparing the actual concentration eta with the parameters in the preset concentration matrix eta 0, so that the using amount of the active carbon can be accurately controlled, the cost is saved while the water-insoluble substance is completely adsorbed, the problem that the bromamine acid contains the water-insoluble substance is solved, and the quality and the yield of the bromamine acid finished product can be effectively improved on the premise of ensuring the process stability.

Further, the secondary detection concentration eta s is compared with the preset standard concentration eta s0 to judge whether the thermal refining reaction of the activated carbon is completed or not, so that whether the activated carbon needs to be added again to ensure that the water-insoluble substance is completely adsorbed or not can be determined, the problem that the bromamine acid contains the water-insoluble substance is solved, and the quality and the yield of the finished bromamine acid product can be effectively improved on the premise of ensuring the process stability.

Furthermore, the concentration difference value delta eta is compared with the parameters in the preset concentration difference value matrix delta eta 0 to determine the amount of the activated carbon to be added again, so that the using amount of the activated carbon can be accurately controlled, the cost is saved while the water-insoluble substances are completely adsorbed, the problem that the bromamine acid contains the water-insoluble substances is solved, and the quality and the yield of the finished bromamine acid can be effectively improved on the premise of ensuring the process stability.

Further, the actual density rho is compared with the parameters in the preset o-dichlorobenzene density matrix rho a0 to determine the amount of the sulfuric acid added again, so that the amount of waste residues in the o-dichlorobenzene after bromination layering can be effectively reduced after the sulfuric acid is added again for bromination reaction, and the quality and yield of the finished product of the bromamine acid are effectively improved.

Furthermore, the invention compares the re-detected density rho s with the preset standard density rho 0 of ortho-dichlorobenzene to determine whether bromination layering is finished or not, so that the layering times can be accurately controlled while the use amount of sulfuric acid is accurately controlled, and the quality and the yield of the finished product of the bromamine acid can be effectively improved.

Furthermore, the quantity of the added water is determined by comparing the density difference value delta rho s with the parameters in the preset density difference value matrix delta rho s0, so that the quantity of waste residues in the new o-dichlorobenzene after secondary layering can be reduced, and the quality and the yield of the finished product of the bromamine acid are effectively improved.

Furthermore, the method can be used as an alternative scheme when the storage capacity of the activated carbon is insufficient or the price is increased so as to ensure that the water-insoluble substances are separated out or adsorbed, so that the finished product of the bromamine acid does not contain the water-insoluble substances, the problem that the bromamine acid contains the water-insoluble substances is solved, and the quality and the yield of the finished product of the bromamine acid are effectively improved on the premise of ensuring the process stability.

Drawings

FIG. 1 is a schematic structural diagram of a novel process unit for synthesizing bromamine acid;

FIG. 2 is a schematic flow diagram of the novel process for synthesizing bromamine acid according to the present invention;

the notation in the figure is: 1. a first reactor; 11. a first feed port; 12. a second feed port; 13. a third feed inlet; 14. a fourth feed port; 15. a dropper port; 16. a density detector; 2. a layering device; 3. a second reactor; 31. a fifth feed port; 32. a quality detector; 4. a third reactor; 41. a sixth feed port; 42. a concentration detector.

Detailed Description

In order that the objects and advantages of the invention will be more clearly understood, the invention is further described below with reference to examples; it should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are only for explaining the technical principle of the present invention, and do not limit the scope of the present invention.

It should be noted that in the description of the present invention, the terms of direction or positional relationship indicated by the terms "upper", "lower", "left", "right", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, which are only for convenience of description, and do not indicate or imply that the device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.

Furthermore, it should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.

Referring to fig. 1 and 2, the new process apparatus for synthesizing bromamine acid of the present embodiment includes:

a first reactor 1 for performing sulfonation and bromination reactions;

the layering device 2 is connected with the reactor and is used for carrying out bromination layering to obtain a brominated material and o-dichlorobenzene;

a second reactor 3 connected to the layering device 2 for performing a neutralization reaction to separate out water-insoluble substances in the brominated material;

a third reactor 4 connected to the second reactor 3 for performing an activated carbon thermal refining reaction to adsorb the water-insoluble substance in the bromamine acid cake;

the first reactor 1 is provided with a first feed port 11, a second feed port 12, a third feed port 13, a fourth feed port 14, a burette port 15 and a density detector 16, wherein the first feed port 11, the second feed port 12, the third feed port 13 and the fourth feed port 14 are all arranged at the upper end of the first reactor 1, the first feed port 11 is used for adding 1-aminoanthraquinone into the first reactor 1 as a raw material, the second feed port 12 is used for adding o-dichlorobenzene into the first reactor 1, the third feed port 13 is used for adding sulfuric acid into the first reactor 1, and the fourth feed port 14 is used for adding sodium bromide and sodium bromate into the first reactor 1; the dripping pipe orifice 15 is arranged on the side surface of the first reactor 1 and is used for dripping chlorosulfonic acid into the first reactor 1; the density detector 16 is arranged in the first reactor 1 and is used for detecting the density of the brominated layered o-dichlorobenzene;

the second reactor 3 is provided with a fifth feeding hole 31 and a quality detector 32, and the fifth feeding hole 31 is arranged at the top of the second reactor 3 and is used for adding liquid caustic soda for neutralization reaction; the quality detector 32 is arranged inside the second reactor 3 and is used for detecting the quality of the brominated material;

the third reactor 4 is provided with a sixth feeding hole 41 and a concentration detector 42, the sixth feeding hole 41 is arranged at the top of the third reactor 4 and is used for adding activated carbon to carry out activated carbon thermal refining reaction; a concentration detector 42 is arranged inside the third reactor 4 for detecting the concentration of the bromamine acid filter cake;

and a central control module (not shown in the figure) which is respectively connected with the devices and is used for controlling the reaction process of the new technology for synthesizing the bromamine acid, and a matrix is arranged in the central control module.

Referring to fig. 1, based on the new process device for synthesizing bromamine acid, the new process for synthesizing bromamine acid in this embodiment includes:

adding 1-aminoanthraquinone serving as a raw material into a first reactor 1 through a first feed port 11, adding o-dichlorobenzene into the first reactor 1 through a second feed port 12, dripping chlorosulfonic acid into the first reactor through a dripping pipe port 15 to perform sulfonation reaction, adding sulfuric acid into the first reactor 1 through a third feed port 13 after the end point of the sulfonation reaction is reached, adding sodium bromide and sodium bromate into the first reactor 1 through a fourth feed port 14 to perform bromination reaction, performing bromination layering in a layering device 2 after the end point of the bromination reaction is reached to obtain a brominated material and o-dichlorobenzene, and distilling and recovering the o-dichlorobenzene;

step two, when the central control module judges that the bromination layering is finished, the brominated materials are placed into a second reactor 3, liquid caustic soda is added through a fifth feeding hole 31 for neutralization reaction so as to separate out water insoluble substances in the brominated materials, and after the neutralization reaction reaches the end point, the brominated materials are sequentially cooled and filtered to obtain a bromamine acid filter cake;

step three, when the central control module judges that the water-insoluble substance is completely separated out, putting the bromamine acid filter cake into a third reactor 4, adding activated carbon through a sixth feeding hole 41 to perform an activated carbon thermal refining reaction so as to adsorb the water-insoluble substance in the bromamine acid filter cake and recover the used waste activated carbon;

step four, sequentially salting out, filter-pressing and drying the bromamine acid filter cake subjected to the activated carbon thermal refining reaction to obtain bromamine acid;

when the bromination reaction end point is reached, taking part of the product after the bromination reaction and putting the part of the product into the layering device 2 for bromination layering, controlling a density detector 16 by a central control module to detect the density of the o-dichlorobenzene after bromination layering, and comparing the actual measured density with the parameters in a preset o-dichlorobenzene density matrix rho a0 to determine the amount of sulfuric acid required to be added again;

when the o-dichlorobenzene is obtained by bromination layering in the layering device 2, the central control module controls the density detector 16 to detect the density of the o-dichlorobenzene in the layering device 2 again and compares the detected density detected again with a preset o-dichlorobenzene standard density to judge whether bromination layering is finished or not; when the central control module judges that the bromination layering is not finished, adding water into the layering device 2 to carry out secondary layering on the o-dichlorobenzene so as to obtain a brominated layering material and new o-dichlorobenzene, and distilling and recovering the new o-dichlorobenzene;

before adding the liquid caustic soda, the central control module controls the quality detector 32 to detect the quality of the brominated material and compares the measured actual quality with the parameters in a preset vulcanized material quality matrix mx0 to determine the amount of the added liquid caustic soda;

when the liquid caustic soda is added, the central control module controls a pH value detector to detect the pH value of the brominated material and compares the detected actual pH value with the preset pH value of the brominated material to judge whether the water-insoluble substance is completely separated out;

before the thermal refining reaction of the activated carbon is carried out, the central control module controls a concentration detector 42 to detect the concentration of the bromamine acid filter cake and compares the measured actual concentration with the parameters in a preset concentration matrix eta 0 to determine the amount of the added activated carbon;

the content of sulfuric acid in the embodiment of the invention is 30%, the control end point of sulfonation reaction is 1-1.2%, and the waste activated carbon is recycled by adopting a water washing and applying mode; adding refined salt in the salting-out process, and discharging wastewater in the filter pressing process;

the central control module is provided with a preset pH value P0 of a brominated material, a preset pH value difference matrix delta P0 and a liquid caustic soda addition matrix mb 0; for the preset pH value difference matrix DeltaP 0, setting DeltaP 0 (DeltaP 1, DeltaP 2 and DeltaP 3), wherein DeltaP 1 represents a first difference of the preset pH value, DeltaP 2 represents a second difference of the preset pH value, DeltaP 3 represents a third difference of the preset pH value, and DeltaP 1 is less than DeltaP 2 and less than DeltaP 3; setting mb0 (mb 1, mb2, mb3 and mb 4) for the liquid caustic soda supplementation matrix mb0, wherein mb1 represents a first liquid caustic soda supplementation, mb2 represents a second liquid caustic supplementation, mb3 represents a third liquid caustic supplementation, mb4 represents a fourth liquid caustic supplementation, and mb1 < mb2 < mb3 < mb 4;

when the liquid caustic soda is added, the actual pH value measured by the pH value detector is marked as P, and when the detection is finished, the central control module compares the actual pH value P with the preset pH value P0 of the brominated material:

if P is more than or equal to P0, the central control module judges that the water-insoluble substance is completely separated out;

if P is less than P0, the central control module judges that the water-insoluble substance is not completely separated out;

when the central control module judges that the precipitation of the water-insoluble substances is incomplete, the central control module calculates the pH value difference value delta P, sets delta P = P0-P, compares the pH value difference value delta P with parameters in a preset pH value difference matrix delta P0 when the calculation is completed,

if delta P is less than delta P1, the central control module sets the amount of the liquid caustic soda added into the fifth feed inlet 31 again to be mb 1;

if the delta P is more than or equal to delta P1 and less than delta P2, the amount of the liquid alkali added into the fifth feeding hole 31 is set to be mb2 by the central control module;

if the delta P is more than or equal to delta P2 and less than delta P3, the amount of the liquid alkali added into the fifth feeding hole 31 is set to be mb3 by the central control module;

if the delta P is equal to or more than the delta P3, the central control module sets the adding amount of the liquid caustic soda again into the fifth feeding hole 31 to be mb 4.

The embodiment of the invention compares the actual density with the parameters in the preset ortho-dichlorobenzene density matrix rho a0 to determine the amount of sulfuric acid required to be added again, compares the density detected again with the preset ortho-dichlorobenzene standard density to determine whether bromination layering is finished, compares the actual quality with the parameters in the preset sulfide quality matrix mx0 to determine the amount of liquid alkali added, compares the actual pH value with the preset pH value of a bromide to determine whether the water-insoluble substance is completely separated out, compares the actual concentration with the parameters in the preset concentration matrix eta 0 to determine the amount of the added active carbon, compares the pH value difference delta P with the parameters in the preset pH value difference matrix delta P0 to determine the amount of the added liquid alkali again, so that the water-insoluble substance can be separated out by adding the liquid alkali and then is adsorbed by adding the active carbon, solves the problem that the bromamine acid contains water-insoluble substances, and further effectively improves the quality and yield of the finished bromamine acid product on the premise of ensuring the process stability.

Specifically, the central control module is further provided with a preset concentration matrix eta 0 and an active carbon addition matrix mt0, wherein eta 0 (eta 1, eta 2 and eta 3) is set for the preset concentration matrix eta 0, eta 1 represents a preset first concentration, eta 2 represents a preset second concentration, eta 3 represents a preset third concentration, and eta 1 is more than eta 2 and less than eta 3; for the activated carbon addition matrix mt0, mt0 (mt 1, mt2, mt3 and mt 4) is set, wherein mt1 represents a first activated carbon addition, mt2 represents a second activated carbon addition, mt3 represents a third activated carbon addition, mt4 represents a fourth activated carbon addition, and mt1 < mt2 < mt3 < mt 4;

in the third step, before the activated carbon thermal refining reaction is performed, the actual concentration measured by the concentration detector 42 is recorded as η, and when the detection is completed, the central control module compares the actual concentration η with parameters in a preset concentration matrix η 0:

if eta is less than eta 1, the central control module sets the amount of the activated carbon added into the sixth feeding hole 41 as mt 1;

if eta 1 is not less than eta < eta 2, the central control module sets the amount of the activated carbon added into the sixth feed port 41 as mt 2;

if eta 2 is not less than eta < eta 3, the central control module sets the amount of the activated carbon added into the sixth feed port 41 as mt 3;

if eta is larger than or equal to eta 3, the central control module sets the amount of the activated carbon added into the sixth feed port 41 as mt 4;

after the central control module controls the sixth feeding hole 41 to add mti amount of activated carbon into the third reactor 4, the central control module controls the concentration detector 42 to detect the concentration of the bromamine acid filter cake again.

According to the embodiment of the invention, the actual concentration eta is compared with the parameters in the preset concentration matrix eta 0 to determine the amount of the added active carbon, so that the using amount of the active carbon can be accurately controlled, the cost is saved while the water-insoluble substance is completely adsorbed, the problem that the bromamine acid contains the water-insoluble substance is solved, and the quality and the yield of the bromamine acid finished product can be effectively improved on the premise of ensuring the process stability.

Specifically, in the third step, when the central control module controls the concentration detector 42 to detect the concentration of the bromamine acid filter cake again, the secondary detection concentration measured by the concentration detector 42 is recorded as η s, meanwhile, the central control module is provided with a preset standard concentration η s0, η s0 is set to be less than η 1, and when the detection and the presetting are completed, the central control module compares the secondary detection concentration η s with a preset standard concentration η s 0:

if eta s is less than or equal to eta s0, the central control module judges that the hot refining reaction of the activated carbon is finished;

if eta s is more than eta s0, the central control module judges that the heat refining reaction of the activated carbon is not completed and controls a sixth feeding port to add the activated carbon again to adsorb the water-insoluble substances in the bromamine acid filter cake.

According to the embodiment of the invention, the secondary detection concentration eta s is compared with the preset standard concentration eta s0 to judge whether the thermal refining reaction of the activated carbon is completed or not, so that whether the activated carbon needs to be added again to ensure that the water-insoluble substance is completely adsorbed or not can be determined, the problem that the bromamine acid contains the water-insoluble substance is solved, and the quality and the yield of the bromamine acid finished product can be effectively improved on the premise of ensuring the process stability.

Specifically, the central control module is further provided with a preset concentration difference matrix delta eta 0, and delta eta 0 (delta eta 1, delta eta 2 and delta eta 3) is set, wherein delta eta 1 represents a first difference of a preset concentration, delta eta 2 represents a second difference of the preset concentration, delta eta 3 represents a third difference of the preset concentration, and delta eta 1 is less than delta eta 2 and less than delta eta 3;

when eta s is larger than eta s0, the central control module calculates the concentration difference delta eta, and the calculation formula is as follows:

△η=（ηs-ηs0）×δ；

wherein δ represents a concentration difference coefficient, and δ = η s/η s0 is set;

when the calculation is finished, the central control module compares the concentration difference value delta eta with the parameters in the preset concentration difference value matrix delta eta 0,

if Δ η <. eta.1, the central control module sets the amount of activated carbon added again at the sixth feed inlet 41 to mh1, setting mh1= mt1 × 0.1;

if the delta eta 1 is less than or equal to the delta eta < delta eta 2, the central control module sets the amount of the activated carbon added again at the sixth feeding hole 41 to mh2, and mh2= mt2 × 0.2 is set;

if the delta eta 2 is less than or equal to the delta eta < delta eta 3, the central control module sets the amount of the activated carbon added again at the sixth feeding hole 41 to mh3, and mh3= mt3 × 0.3 is set;

if Δ η ≧ Δ η 3, the central control module sets the amount of activated carbon to be added again at the sixth feed inlet 41 to mh4, setting mh4= mt4 × 0.4;

wherein mti represents the ith addition of activated carbon, and i =1,2,3,4 is set.

According to the embodiment of the invention, the concentration difference value delta eta is compared with the parameters in the preset concentration difference value matrix delta eta 0 to determine the amount of the activated carbon to be added again, so that the using amount of the activated carbon can be accurately controlled, the cost is saved while the water-insoluble substance is completely adsorbed, the problem that the bromamine acid contains the water-insoluble substance is solved, and the quality and the yield of the bromamine acid finished product can be effectively improved on the premise of ensuring the process stability.

Specifically, the central control module is further provided with a preset o-dichlorobenzene density matrix rho a0 and a sulfuric acid addition matrix ml 0; setting rho a0 (rho a1, rho a2 and rho a 3) for the preset ortho-dichlorobenzene density matrix rho a0, wherein rho a1 represents a preset ortho-dichlorobenzene first density, rho a2 represents a preset ortho-dichlorobenzene second density, rho a3 represents a preset ortho-dichlorobenzene third density, and rho a1 & lt rho a2 & lt rho a 3; for the sulfuric acid addition matrix ml0, ml0 (ml 1, ml2, ml3, ml 4) is set, wherein ml1 represents a first addition of sulfuric acid, ml2 represents a second addition of sulfuric acid, ml3 represents a third addition of sulfuric acid, ml4 represents a fourth addition of sulfuric acid, ml1 < ml2 < ml3 < ml 4;

in the first step, when a part of the mixture is put into the layering device 2 for bromination layering, the actual density measured by the density detector 16 is recorded as ρ, and when the detection is completed, the central control module compares the actual density ρ with the parameters in a preset o-dichlorobenzene density matrix ρ a 0:

if rho is more than rho a1, setting the amount of sulfuric acid added into the third feed port 13 again to be ml1 by the central control module;

if rho is not less than rho 1 and is more than rho a2, the central control module sets the amount of sulfuric acid added into the third feed port 13 again to be ml 2;

if rho is not less than rho 2 and is more than rho a3, the central control module sets the amount of sulfuric acid added into the third feed port 13 to be ml3 again;

if the rho is larger than or equal to rho a3, setting the amount of sulfuric acid added into the third feed port 13 again to be ml4 by the central control module;

the central control module controls the third feed port 13 to add the sulfuric acid of mli amount again, and then the bromination reaction is continued in the first reactor 1, and i =1,2,3,4 is set.

According to the embodiment of the invention, the actual density rho is compared with the parameters in the preset o-dichlorobenzene density matrix rho a0 to determine the amount of the sulfuric acid added again, so that the amount of waste residues in the o-dichlorobenzene after bromination layering can be effectively reduced after the sulfuric acid is added again for bromination reaction, and the quality and yield of bromamine acid finished products are effectively improved.

Specifically, when the central control module controls the third feed port 13 to add mli sulfuric acid again and perform bromination layering in the layering device 2 to obtain the o-dichlorobenzene, i =1,2,3,4 is set, the density detected again by the density detector 16 is recorded as ρ s, meanwhile, the central control module is provided with a preset o-dichlorobenzene standard density ρ 0, ρ 0 > ρ a4, and when the detection and the setting are completed, the central control module compares the density ρ s detected again with the preset o-dichlorobenzene standard density ρ 0:

if rho s is larger than or equal to rho 0, the central control module judges that the bromination layering is finished;

and if rho s is less than rho 0, the central control module judges that the bromination layering is not finished.

According to the embodiment of the invention, whether bromination layering is finished or not is determined by comparing the redetected density rho s with the preset standard density rho 0 of ortho-dichlorobenzene, so that the layering times can be accurately controlled while the use amount of sulfuric acid is accurately controlled, and the quality and yield of a finished product of bromamine acid can be effectively improved.

Specifically, the central control module is further provided with a preset density difference value matrix delta rho 0 and a water adding quantity matrix mj 0; for the preset density difference matrix Δ ρ s0, Δ ρ s0 (Δ ρ s1, Δ ρ s2, Δ ρ s 3) is set, where Δ ρ s1 represents a preset first density difference, Δ ρ s2 represents a preset second density difference, Δ ρ s3 represents a preset third density difference, and Δ ρ s1 < [ Δ ρ s2 < [ Δ ρ s3 ]; setting mj0 (mj 1, mj2, mj3 and mj 4) for the water adding amount matrix mj0, wherein mj1 represents a first water adding amount, mj2 represents a second water adding amount, mj3 represents a third water adding amount, mj4 represents a fourth water adding amount, and mj1 < mj2 < mj3 < mj 4;

when the central control module judges that the bromination layering is not finished, the central control module calculates a density difference value delta rho s, and the water adding amount is calculated as follows:

△ρs=（ρ0-ρs）×σ；

where σ denotes a density difference coefficient, and σ = ρ 0/ρ s is set;

when the calculation is finished, the central control module compares the density difference value delta rho s with the parameters in the preset density difference value matrix delta rho s0,

if the delta rho s is less than the delta rho s1, the central control module sets the water adding amount in the layered device to mj 1;

if the delta rho s1 is less than or equal to the delta rho s2, the central control module sets the water adding amount in the layering device to mj 2;

if the delta rho s2 is less than or equal to the delta rho s3, the central control module sets the water adding amount in the layering device to mj 3;

if the delta rho s is not less than the delta rho s3, the central control module sets the water adding amount in the layered device to mj 4. According to the embodiment of the invention, the density difference delta rho s is compared with the parameters in the preset density difference matrix delta rho s0 to determine the amount of the added water, so that the amount of waste residues in the new o-dichlorobenzene after secondary layering can be reduced, and the quality and yield of the finished product of the bromamine acid are effectively improved.

Specifically, the central control module is further provided with a preset vulcanizing material mass matrix mx0, and mx0 (mx 1, mx2, mx 3) is set, wherein mx1 represents a first preset vulcanizing material mass, mx2 represents a second preset vulcanizing material mass, mx3 represents a third preset vulcanizing material mass, and mx1 < mx2 < mx 3;

in the second step, before the liquid caustic soda is added, the actual mass measured by the mass detector 32 is recorded as mx, and when the detection is completed, the central control module compares the actual mass mx with parameters in a preset vulcanizing material mass matrix mx 0:

if mx is less than mx1, the central control module determines that the amount of the liquid caustic soda added to the fifth feed port 31 is my1, and sets my1=10 xmb 1;

if mx1 is not less than mx and is less than mx2, the central control module determines that the amount of the liquid alkali added into the fifth feed port 31 is my2, and my2=20 xmb 2 is set;

if mx2 is not less than mx and is less than mx3, the central control module determines that the amount of the liquid alkali added into the fifth feed port 31 is my3, and my3=30 xmb 3 is set;

if mx is larger than or equal to mx3, the central control module judges that the amount of the liquid caustic soda added into the fifth feed port 31 is my4, and my4=10 xmb 4 is set;

wherein myi represents the i th supplementary amount of the liquid caustic soda, and i =1,2,3,4 is set.

According to the embodiment of the invention, the actual mass mx is compared with the parameters in the preset vulcanizing material mass matrix mx0 to determine the amount of the added liquid caustic soda, so that the amount of the added liquid caustic soda can be accurately controlled, and the quality and yield of finished bromamine acid are effectively improved on the premise of ensuring the process stability.

Specifically, when the central control module determines that the thermal refining reaction of the activated carbon is not completed, the amount of the activated carbon can be not added, and the amount of the filter cloth can be directly adjusted in the subsequent filter pressing process to separate out water-insoluble substances.

The embodiment of the invention can be used as an alternative scheme when the storage capacity of the activated carbon is insufficient or the price is increased to ensure that the water-insoluble substances are separated out or adsorbed, so that the finished bromamine acid product does not contain the water-insoluble substances, the problem that the bromamine acid contains the water-insoluble substances is solved, and the quality and the yield of the bromamine acid product are effectively improved on the premise of ensuring the process stability.

Example 1

Brominating the material after layering through bromination, and performing different neutralization pH tests:

taking a brominated layered material layer, adding alkali to neutralize the brominated layered material layer respectively until the pH is 6-7 and the pH =9, heating the brominated layered material layer to boil, re-measuring the pH, finding that the pH is reduced in different degrees, adding liquid alkali to adjust the pH to a specified value, cooling the mixed material to 50 ℃, filtering the mixed material, taking a filter cake to perform insoluble substance test, and observing whether insoluble substances are separated out and the separated amount; and neutralizing the salting-out filtrate at pH6-7 with liquid alkali to pH9.35, filtering, and observing whether insoluble substances which are not completely separated out are separated out again under alkaline conditions.

And (4) conclusion:

when the pH is adjusted to 6-7 by neutralization, a trace amount of black insoluble substances exist in the bromamine acid filter cake;

when the pH is adjusted to 9 by neutralization, more brown-black insoluble substances exist in the bromamine acid filter cake;

neutralizing the salting-out filtrate with pH6-7, adding alkali, and filtering to obtain small amount of black insoluble substances;

combining several points, insoluble matters are separated out at 6-7, but the insoluble matters are not completely separated out and are completely separated out under the alkaline condition.

Example 2

And (3) testing materials after neutralization and heat refining:

testing the PH value and the water insoluble substance of the material after thermal refining, wherein the PH value of the material after thermal refining is about 4-5, and after testing, when no water insoluble substance exists, and the PH value is adjusted to be =7 by adding alkali, a large amount of insoluble substances appear; it was thus found that the insoluble matter was always present in the system, and that the insoluble matter was dissolved at a pH of 4-5, and that salting-out was carried out while controlling the pH, so that the insoluble matter was left in the salting-out solution.

Example 3

(1) Refining and blanking of active carbon

Dissolving about 68g of the first-extract activated carbon in 200ml of hot water, adding hydrochloric acid, filtering, measuring the pH of the filtrate to be =1.6, adding liquid alkali, and separating out a large amount of black insoluble substances; the results show that more insoluble matter is adsorbed by the activated carbon.

(2) Blank test for activated carbon

Taking 30g of fresh activated carbon, putting into 200ml of water, measuring the pH of the water to be 8.05 before adding the activated carbon, measuring the pH to be 2.7 after adding the activated carbon, adding hydrochloric acid, filtering, measuring the pH of filtrate to be 0.4, adding liquid alkali to adjust the pH to be 8-9, and performing suction filtration to obtain a trace of yellow-green insoluble substances; according to analysis, trace insoluble substances in a pilot test active carbon blank test are negligible according to the total amount of 30kg of active carbon and 5000kg of active carbon in a workshop volume;

the two groups of experiments show that the activated carbon has better adsorption effect on insoluble substances.

Comprehensively, insoluble substances are reaction byproducts, and the method for removing the insoluble substances is to adjust the pH value to about 8 during neutralization, fully separate out the insoluble substances, maintain the pH value above 7 during the addition of the activated carbon thermal refining, and adsorb the completely separated insoluble substances in the activated carbon.

So far, the technical solutions of the present invention have been described in connection with the preferred embodiments shown in the drawings, but it is easily understood by those skilled in the art that the scope of the present invention is obviously not limited to these specific embodiments. Equivalent changes or substitutions of related technical features can be made by those skilled in the art without departing from the principle of the invention, and the technical scheme after the changes or substitutions can fall into the protection scope of the invention.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention; various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.