US3079404A - Process for manufacturing alpha-anthraquinone disulfonate containing low amounts of mercury - Google Patents
Process for manufacturing alpha-anthraquinone disulfonate containing low amounts of mercury Download PDFInfo
- Publication number
- US3079404A US3079404A US17787A US1778760A US3079404A US 3079404 A US3079404 A US 3079404A US 17787 A US17787 A US 17787A US 1778760 A US1778760 A US 1778760A US 3079404 A US3079404 A US 3079404A
- Authority
- US
- United States
- Prior art keywords
- anthraquinone
- mercury
- sulfonation
- acid
- dipotassium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 15
- 229910052753 mercury Inorganic materials 0.000 title description 49
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title description 48
- 238000004519 manufacturing process Methods 0.000 title description 6
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 19
- 238000006277 sulfonation reaction Methods 0.000 claims description 14
- 150000004056 anthraquinones Chemical class 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 12
- -1 ANTHRAQUINONE COMPOUND Chemical class 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- IJNPIHLZSZCGOC-UHFFFAOYSA-N 9,10-dioxoanthracene-1,8-disulfonic acid Chemical compound O=C1C2=CC=CC(S(O)(=O)=O)=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O IJNPIHLZSZCGOC-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012736 aqueous medium Substances 0.000 claims description 4
- 229940041669 mercury Drugs 0.000 description 48
- QBPFLULOKWLNNW-UHFFFAOYSA-N chrysazin Chemical compound O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O QBPFLULOKWLNNW-UHFFFAOYSA-N 0.000 description 30
- 239000002253 acid Substances 0.000 description 11
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 11
- 229960001577 dantron Drugs 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 7
- 239000012286 potassium permanganate Substances 0.000 description 7
- KIEOKOFEPABQKJ-UHFFFAOYSA-N sodium dichromate Chemical compound [Na+].[Na+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KIEOKOFEPABQKJ-UHFFFAOYSA-N 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- OZTBHAGJSKTDGM-UHFFFAOYSA-N 9,10-dioxoanthracene-1,5-disulfonic acid Chemical compound O=C1C=2C(S(=O)(=O)O)=CC=CC=2C(=O)C2=C1C=CC=C2S(O)(=O)=O OZTBHAGJSKTDGM-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- BTLXPCBPYBNQNR-UHFFFAOYSA-N 1-hydroxyanthraquinone Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2O BTLXPCBPYBNQNR-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- WQUQVOTVFCDTEH-UHFFFAOYSA-N 1,5-dioxoanthracene-2,3-disulfonic acid Chemical compound C1=CC(=O)C2=CC3=CC(S(=O)(=O)O)=C(S(O)(=O)=O)C(=O)C3=CC2=C1 WQUQVOTVFCDTEH-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- WWPPXDOOKMWVDN-UHFFFAOYSA-N 3-amino-3,4-dihydro-1h-1,5-naphthyridin-2-one Chemical compound C1=CC=C2NC(=O)C(N)CC2=N1 WWPPXDOOKMWVDN-UHFFFAOYSA-N 0.000 description 1
- PTKWYSNDTXDBIZ-UHFFFAOYSA-N 9,10-dioxoanthracene-1,2-disulfonic acid Chemical class C1=CC=C2C(=O)C3=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C3C(=O)C2=C1 PTKWYSNDTXDBIZ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000008645 Chenopodium bonus henricus Nutrition 0.000 description 1
- 244000138502 Chenopodium bonus henricus Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- HGFAOWBEMBVMSS-UHFFFAOYSA-L dipotassium;9,10-dioxoanthracene-1,2-disulfonate Chemical compound [K+].[K+].C1=CC=C2C(=O)C3=C(S([O-])(=O)=O)C(S(=O)(=O)[O-])=CC=C3C(=O)C2=C1 HGFAOWBEMBVMSS-UHFFFAOYSA-L 0.000 description 1
- 235000021463 dry cake Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 229960001156 mitoxantrone Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/26—Quinones containing groups having oxygen atoms singly bound to carbon atoms
- C07C50/34—Quinones containing groups having oxygen atoms singly bound to carbon atoms the quinoid structure being part of a condensed ring system having three rings
Definitions
- This invention relates to an improved process for preparing a-anthraquinone sulfonates, and derivatives thereof particularly 1,8-dihydroxy anthraquinone (Chrysazine), containing low amounts of mercury.
- Chisazine 1,8-dihydroxy anthraquinone
- Patent 2,742,484 of April 17, 1956 that when the sulfonation is effected in the presence of mercury or mercury compounds as described for example in U.S Patent 742,910 of November 3, 1903, sulfonation in the a-position is favored, whereas if the sulfonation is effected in the absence of mercury, then sulfonation in the p-position is favored.
- a mercury catalyst in the sulfonation of anthraquinone to produce 1- anthraquinone sulfonic acid and a,a'-anthraquinone disulfonic acids, e.g. the 1,5- or 1,8-anthraquinone disulfonic acid or their salts.
- the resulting a-sulfonic acid or salt or a,u'-disulfonic acid or salt still contains substantial amounts of mercury, which is usually about 1% or higher. This mercury is so combined in the 01- or a,a-anthraquinone sulfonic acid that it is extremely difficult to remove.
- the mercury content of ozanthraquinone sulfonates obtained by sulfonation of anthraquinone in the presence of mercury, and also derivatives of such a-an-thraquinone sulfonates (e.g. 1,8- dihydroxy anthraquinone) can be substantially reduced by heating the mercury containing m-anthraquinone disulfonate (or derivative) in the presence of an oxidizing agent.
- an alkali metal bichromate or permanganate e.g.
- sodium or potassium bichromate or sodium or potassium permanganate as the oxidizing agent, however, other oxidizing agents such as nitric acid, hydrogen peroxide, sodium or potassium hypochlorite, chlorine, ammonium-, potassiumor sodium persulfate and the like may be used.
- Example 1 50 g. of paste material of dipotassium 1,8-anthraquinone disulfonate (containing about 18 g. of 100% dipotassium 1,8-anthraquinone disulfonate having a mercury content of about 1% and which had been recovered by treating with potassium chloride the acid liquor from 1,5-anthraquinone disulfonic acid manufacture after the 1,5-isomer had been separated in a manner similar to the procedure given in FIAT Report #1016, page 6), was slurried in 50 cc. of water and 10 cc. of a 5% solution of potassium permanganate in water was added. The mixture was heated to 95100 C.
- dipotassium 1,8-anthraquinone disulfonate containing about 18 g. of 100% dipotassium 1,8-anthraquinone disulfonate having a mercury content of about 1% and which had been recovered by treating with potassium chloride the acid liquor from 1,5-anthraquinone
- Example 2 The foregoing experiment was repeated using, however, in place of the potassium permanganate 10 cc. of a 5% solution of sodium bichromate in water. The analysis of the dried dipotassium 1,8-anthraquinone disulfonate which was recovered showed that it had a mer cury content of 0.077%. The product of both Example 1 and Example 2 when employed for the production of Chrysazine gave a material meeting the specifications of the National Formulary, i.e. Chrysazine containing less than 50 ppm. mercury.
- the processof the present invention can be applied to dipotassium anthraquinone disulfonate in a concentrated form
- the process of the present invention can beap'plied to the acid liquors containing the mercury containing 1,8- anthraquinone disulfona-te having a high mercury content remaining after removal of 1,5-anthraquinone disulfonate from the products produced in the disulfonation of an-thraquinone in the presence of mercury.
- Example 3 925 cc. of the acid liquor from 1,5-anthraquinone disulfonic acid manufacture after the 1,5-isomer had been separated in a manner similar to the procedure given in FIAT Report #1016, page 6, and which consisted largely of mercury containing 1,8-anthraquinone disulfonic acid and a small amount of unsulfonated anthraquinone was diluted with water to a volume of 2925 cc. The thus diluted liquor was heated to 100 C. and 7.5 grams of sodium bichromate added thereto and the mixture stirred for /2 hour at 100 C.
- the material was then filtered hot on a fritted glass filter and a small amount of undissolved, unsulfonated anthraquinone thus filtered out and discarded.
- the 1,8-anthraquinone disulfonic acid was then recovered in the form of its dipotassium salt by cooling the filtrate to C. and adding at 75 C. in /2 hour 45.5 g. of potassum chloride.
- the liquor was tested for complete precipitation of the insoluble potassium salt by adding a few crystals of potassum chloride to 5-10 cc. portions of the filter liquor. When the test showed complete precipitation in the batch, the batch was cooled to 55 C. and filtered on a fritted glass filter.
- the dipotassium 1,8-anthraquinone disulfonate containing 0.23% mercury was then used as base material for preparing Chrysazine in the customary manner by autoolaving with lime followed by dilution, acidification, boil- Example 4
- anthraquinone compound selected from the group consisting of l,S-dihydroxyanthraquinone and l,8-anthraquinone disulfonic acid and its salts which have been produced by the sulfonation of anthraquinone in the presence of a mercury catalyst which comprises heating in an aqueous medium said anthraquinone compound together with a small amount of an inorganic oxidizing agent and separating said anthraquinone compound substantially tree of mercury from said aqueous medium.
- the method of reducing the mercury content of 1,8-anthraquinone disulfonic acid dipotassium salt produced by sulfonation of anthraquinone in the presence of a mercury catalyst which comprises heating an aqueous slurry of such mercury containing dipotassium l,8-anthraquinone disulfonate with a small amount of an oxidizing agent selected from the group consisting of nitric acid,
- the method of reducing the mercury content of 1,8-dihydroxy anthraquinone produced from a 1,8-anthraquinone disultonic acid which in turn was produced by sulfonation of anthraquinone in the presence of a mercury catalyst which comprises heating an aqueous slurry of said 1,8-dihydroxy anthraquinone with a small amount of an oxidizing agent selected from the group consisting of nitric acid, potassium permanganate and sodium bichromate and separating said 1,8-dihydroxy anthraquinone substantially free of mercury from the aqueous phase.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
ttea
ice
, 3,079,404 PRGCESS FOR MANUFACTURING u-ANTHIRA- QUINONE DESULFONATE CBNTAINING LQW AMOUNTS F MERCURY Robert D. Donaldson, Metnchen, and Eidred V. Welch, West-field, N1, assignors to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Mar. 28, 1960, Ser. N 17,787 7 Claims. (Cl. 260-670) This invention relates to an improved process for preparing a-anthraquinone sulfonates, and derivatives thereof particularly 1,8-dihydroxy anthraquinone (Chrysazine), containing low amounts of mercury. In the sulfonation of anthraquinone, it is known as more fully described in US. Patent 2,742,484 of April 17, 1956, that when the sulfonation is effected in the presence of mercury or mercury compounds as described for example in U.S Patent 742,910 of November 3, 1903, sulfonation in the a-position is favored, whereas if the sulfonation is effected in the absence of mercury, then sulfonation in the p-position is favored.
Accordingly, it is common to employ a mercury catalyst in the sulfonation of anthraquinone to produce 1- anthraquinone sulfonic acid and a,a'-anthraquinone disulfonic acids, e.g. the 1,5- or 1,8-anthraquinone disulfonic acid or their salts. However, the resulting a-sulfonic acid or salt or a,u'-disulfonic acid or salt still contains substantial amounts of mercury, which is usually about 1% or higher. This mercury is so combined in the 01- or a,a-anthraquinone sulfonic acid that it is extremely difficult to remove. Accordingly, there has been considerable demand in the art for an inexpensive process by which the amount of mercury contained in ocor a,a'-anthraquinone sulfonic acids or their salts, obtained by the sulfonation of anthraquinone in the presence of mercury, may be reduced to a minimum. The removal of the mercury has been particularly important in the case of 1,8-anthraquinone disulfonic acid, since this is employed as an intermediate for the preparation of 1,8- dihydroxy anthraquinone, also called Chrysazine, which is employed for medicinal uses. Thus, the National Formulary (1955) has imposed a strict specification requiring that 1,8-dihydroxy anthraquinone (Chrysazine) contain not more than 50 p.p.-m. of mercury. In order to produce Chyrsazine meeting these specifications from 1,8-anthraquinone disulfonic acid or its salt, it has been found necessary to employ 1,8-anthraquinone disulfonate containing less than 0.25% mercury.
We have now found that the mercury content of ozanthraquinone sulfonates, obtained by sulfonation of anthraquinone in the presence of mercury, and also derivatives of such a-an-thraquinone sulfonates (e.g. 1,8- dihydroxy anthraquinone) can be substantially reduced by heating the mercury containing m-anthraquinone disulfonate (or derivative) in the presence of an oxidizing agent. We particularly prefer to use an alkali metal bichromate or permanganate, e.g. sodium or potassium bichromate or sodium or potassium permanganate as the oxidizing agent, however, other oxidizing agents such as nitric acid, hydrogen peroxide, sodium or potassium hypochlorite, chlorine, ammonium-, potassiumor sodium persulfate and the like may be used.
The details of the present invention will be apparent from the following specific examples of preferred embodiments thereof.
Example 1 50 g. of paste material of dipotassium 1,8-anthraquinone disulfonate (containing about 18 g. of 100% dipotassium 1,8-anthraquinone disulfonate having a mercury content of about 1% and which had been recovered by treating with potassium chloride the acid liquor from 1,5-anthraquinone disulfonic acid manufacture after the 1,5-isomer had been separated in a manner similar to the procedure given in FIAT Report #1016, page 6), was slurried in 50 cc. of water and 10 cc. of a 5% solution of potassium permanganate in water was added. The mixture was heated to 95100 C. for 1 hour, then cooled to room temperature and the dipotassium 1,8- anthraquinone disulfonate recovered by filtration, the filter cake being washed with water until free of permanganate. The cake was then dried in a vacuum oven at 85-90 C. and on analysis the dry cake was found to contain 0.093% mercury.
Example 2 The foregoing experiment was repeated using, however, in place of the potassium permanganate 10 cc. of a 5% solution of sodium bichromate in water. The analysis of the dried dipotassium 1,8-anthraquinone disulfonate which was recovered showed that it had a mer cury content of 0.077%. The product of both Example 1 and Example 2 when employed for the production of Chrysazine gave a material meeting the specifications of the National Formulary, i.e. Chrysazine containing less than 50 ppm. mercury.
While as indicated inthe above examples, the processof the present invention can be applied to dipotassium anthraquinone disulfonate in a concentrated form, it has been found as illustrated by the following example that the process of the present invention can beap'plied to the acid liquors containing the mercury containing 1,8- anthraquinone disulfona-te having a high mercury content remaining after removal of 1,5-anthraquinone disulfonate from the products produced in the disulfonation of an-thraquinone in the presence of mercury.
Example 3 925 cc. of the acid liquor from 1,5-anthraquinone disulfonic acid manufacture after the 1,5-isomer had been separated in a manner similar to the procedure given in FIAT Report #1016, page 6, and which consisted largely of mercury containing 1,8-anthraquinone disulfonic acid and a small amount of unsulfonated anthraquinone was diluted with water to a volume of 2925 cc. The thus diluted liquor was heated to 100 C. and 7.5 grams of sodium bichromate added thereto and the mixture stirred for /2 hour at 100 C. The material was then filtered hot on a fritted glass filter and a small amount of undissolved, unsulfonated anthraquinone thus filtered out and discarded. The 1,8-anthraquinone disulfonic acid was then recovered in the form of its dipotassium salt by cooling the filtrate to C. and adding at 75 C. in /2 hour 45.5 g. of potassum chloride. The liquor was tested for complete precipitation of the insoluble potassium salt by adding a few crystals of potassum chloride to 5-10 cc. portions of the filter liquor. When the test showed complete precipitation in the batch, the batch was cooled to 55 C. and filtered on a fritted glass filter. The filter cake (dipotassium 1,8-anthraquinone disulfonate) was Washed 8 times with 50 cc. portions of 1.5% potassium chloride solution in water at room temperature. The filter cake was sucked as dry as possible, then dried in a vacuum oven at -90 C. The dry filter cake on analysis had a mercury content of 0.23%. In a control run in which the treatment with sodium bichrom ate was omitted, the recovered dipotassium 1,8-anthraquinone disulfonate contained 1.01% mercury. The dipotassium 1,8-anthraquinone disulfonate containing 0.23% mercury was then used as base material for preparing Chrysazine in the customary manner by autoolaving with lime followed by dilution, acidification, boil- Example 4 To astainless steel kettle equipped with agitator there was charged 3,330parts by weight of water and 676 parts by Weight of dry powder Chrysazine (1,8-dihydroxy anthraquinone) which was off standard since analysis showed that it contained 288 ppm. of mercury. There was also added 1 /2 parts by weight of the nonionic surface active agent obtained by condensing nonylphenol with about moles of ethylene oxide to aid in wetting out the Chrysazine. The mixture was stirred until the Chrysazine was homogenously dispersed in the water. There was then added 186 parts by weight of 26 B. nitric acid-(35.5% HNOs), Or 65 parts by weight of 100% HNO so as to give 1.85% nitric acid concentration in the kettle. The mixture was heated to 98 C. and held at this temperature while stirring for one hour. The charge in the kettle was then transferred to a filter and the kettle washed with about 100 parts by weight of hot water. After filtering, the filter cake was washed 3 times with 500 parts by weight of hot water until the filtrate was neutral to Congo red paper. The filter cake was sucked as dry as possible and the filter cake stored in lined drums. There was recovered 665 parts by weight (dry basis) of 1,8-dihydroxy anthraquinone or 98.5% of theory which analysis showed contained 40 ppm. of mercury.
While the present invention has thus far been described in connection with the removal of mercury from 1,8-d.i hydroxy anth-raquinone. and 1,8-anthraquinone disulfonic acids and its salts, since these materials are used for pharmaceutical purposes or as an intermediate for the preparation of a pharmaceutical, 1,8-dihydroxy anthraquinone, (Chrysazine), respectively, which must have a mercury content of less thanSO p.p.m., it will be understood that the process of the present invention can be applied to reduction of the mercury content of other a-su-lfonated anthraquinones which have been produced by sulfonation of anthraquinone in the presence of a mercury catalyst. Thus by similar procedures the mercmy content of l-anthraquinone sulfonic acid or its salts, 1,5-anthraquinone disulfonic acid or its salts, or the mixed 1,5 and 1,8-anthraquinone disulfonic acids or salts can be reduced by treatment with an oxidizing agent in accordance with the present invention to reduce the mercury content of each of these isomers so that either the mixed isomers of low mercury content can be obtained or the individual isomers, each having a low mercury content, may be separated from this mixture,
We claim:
1. The method of reducing the mercury content of an anthraquinone compound selected from the group consisting of l,S-dihydroxyanthraquinone and l,8-anthraquinone disulfonic acid and its salts which have been produced by the sulfonation of anthraquinone in the presence of a mercury catalyst which comprises heating in an aqueous medium said anthraquinone compound together with a small amount of an inorganic oxidizing agent and separating said anthraquinone compound substantially tree of mercury from said aqueous medium.
2. The method as defined in claim 1 wherein the oxidizing agent specified is potassium permanganate.
3. The method as defined in claim 1 wherein the oxidizing agent specified is sodium bichromate.
4. The method as defined in claim 1 wherein the oxidizing agent specified is nitric acid.
5. The method of reducing the mercury content of 1,8-anthraquinone disulfonic acid dipotassium salt produced by sulfonation of anthraquinone in the presence of a mercury catalyst which comprises heating an aqueous slurry of such mercury containing dipotassium l,8-anthraquinone disulfonate with a small amount of an oxidizing agent selected from the group consisting of nitric acid,
potassium permanganate and sodium bichromate and separating said (ii-potassium 1,8-anthraquinone sulfonate substantially free of mercury from the aqueous phase.
6. The method of reducing the mercury content of (ll-potassium 1,8-anthraquinone disulfonate from the acid liquors remaining after the removal of 1,5-anthraquinone disulfonic acid from the anthraquinone disulfonic acids produced by sulfonation of anthraquinone in the presence of a mercury catalyst which comprises heating said acid liquors with a small amount of an oxidizing agent selected from the group consisting of nitric acid, potassium permanganate and sodium bichromate, adding potassium chloride to the thus treated mixture to precipitate the dipotassium 1,8-anthraquinone disulfonate and separating the thus precipitated dipotassium salt substantially free from mercury from the aqueous phase.
7. The method of reducing the mercury content of 1,8-dihydroxy anthraquinone produced from a 1,8-anthraquinone disultonic acid which in turn was produced by sulfonation of anthraquinone in the presence of a mercury catalyst, which comprises heating an aqueous slurry of said 1,8-dihydroxy anthraquinone with a small amount of an oxidizing agent selected from the group consisting of nitric acid, potassium permanganate and sodium bichromate and separating said 1,8-dihydroxy anthraquinone substantially free of mercury from the aqueous phase.
References Cited in the file of this patent FOREIGN PATENTS 470,503 Ge many Jan. 18, 1929
Claims (1)
1. THE METHOD OF REDUCING THE MERCURY CONTENT OF AN ANTHRAQUINONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF 1,8-DIHYDROXYANTHERAQUINONE AND 1,8-ANTHRAQUINONE DISULFONIC ACID AND ITS SALTS WHICH HAVE BEEN PRODUCED BY THE SULFONATION OF ANTHRAQUINONE IN THE PRESENCE OF A MERCURY CATALYST WHICH COMPRISES HEATING IN AN AQUEOUS MEDIUM SAID ANTHRAQUINONE COMPOUND TOGETHER WITH A SMALL AMOUNT OF AN INORGANIC OXIDIZING AGENT AND SEPARATING SAID ANTHRAQUINONE COMPOUND SUBSTANTIALLY FREE OF MERCURY FROM SAID AQUEOUS MEDIUM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17787A US3079404A (en) | 1960-03-28 | 1960-03-28 | Process for manufacturing alpha-anthraquinone disulfonate containing low amounts of mercury |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17787A US3079404A (en) | 1960-03-28 | 1960-03-28 | Process for manufacturing alpha-anthraquinone disulfonate containing low amounts of mercury |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3079404A true US3079404A (en) | 1963-02-26 |
Family
ID=21784545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US17787A Expired - Lifetime US3079404A (en) | 1960-03-28 | 1960-03-28 | Process for manufacturing alpha-anthraquinone disulfonate containing low amounts of mercury |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3079404A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE470503C (en) * | 1926-12-07 | 1929-01-18 | I G Farbenindustrie Akt Ges | Process for the preparation of anthraquinone derivatives |
-
1960
- 1960-03-28 US US17787A patent/US3079404A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE470503C (en) * | 1926-12-07 | 1929-01-18 | I G Farbenindustrie Akt Ges | Process for the preparation of anthraquinone derivatives |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2141893A (en) | Trifluoromethyl-aryl-sulphonic acids and a process of preparing them | |
| US2219330A (en) | Phthalocyanine sulphonic acid chloride | |
| US1963383A (en) | Process of sulphonating anthraquinone and its derivatives | |
| US3079404A (en) | Process for manufacturing alpha-anthraquinone disulfonate containing low amounts of mercury | |
| US2598692A (en) | Manufacture of sodium 2, 4, 5-trichlorophenoxyacetate | |
| US1759554A (en) | Process for preparing 6-chloro-2-nitro-1-methylbenzene-4-sulphonic acid | |
| US3163659A (en) | Process for the manufacture of 4, 5-dichloro- and 4, 5-dibromo-naphthalene-1, 8-dicarboxylic acids and their anhydrides | |
| US2018813A (en) | Mu-arylene-tmazole and arylene | |
| US2575155A (en) | Manufacture of polyhydroxy anthraquinone sulfonic acids | |
| US2385899A (en) | Production of diphenyl sulphones | |
| US2378168A (en) | Process for preparing 2, 6-dintro-4-sulpho-toluene | |
| US2484791A (en) | Purification of nu-substituted sulfanilamides | |
| US2999869A (en) | Alkali metal salts of alpha,alpha'-anthraquinone disulfonates | |
| US1452481A (en) | Manufacture of 1.4 naphthol sulphonic acid | |
| US2050657A (en) | Process of preparing 1, 4, 5, 8-napthalene-tetra-carboxylic acid | |
| US2360010A (en) | Process for the sulphonation of alpha - aminoanthraquinone compounds | |
| US2227508A (en) | Preparation of titanium gluconate | |
| US3888885A (en) | Process for the preparation of 4-chloro-naphthalic acid anhydride | |
| US2301762A (en) | Preparation of metal salts of organic polybasic acids | |
| US2418318A (en) | Process for the preparation of bzi-chlorobenzanthrone | |
| US2751383A (en) | Fluorescent heterocyclic compounds and process for their manufacture | |
| US1594547A (en) | Production of alpha-nitronaphthalene-beta-sulphonic acids | |
| US1880593A (en) | Aminocarbazole-sulphonic acid | |
| US2379032A (en) | Process for the preparation of naphthalic acids | |
| US2124863A (en) | Methyl-aminonaphthalene-sulphonic acids and process of preparing them |