PROCESS FOR THE PREPARATION OF AROMATIC COMPOUNDS

Abstract

A process for the preparation of small aromatic compounds from black liquor comprising: providing black liquor that derives from alkaline treatment of wood chips; subjecting the black liquor to a pyrolysis treatment to yield a pyrolysed black liquor gas and a solid mass comprising char and salts in a first reactor, wherein the salts substantially derive from the treatment of black liquor; contacting at least part of the pyrolysed black liquor gas with a catalyst in a second reactor, which is different from the first reactor to provide a conversion treatment to yield a conversion product; and recovering small aromatic compounds from the conversion product.

Claims

1. A process for the preparation of small aromatic compounds from black liquor comprising: providing black liquor that derives from alkaline treatment of wood chips; subjecting the black liquor to a pyrolysis treatment to yield a pyrolysed black liquor gas and a solid mass comprising char and salts in a first reactor, wherein the salts substantially derive from the treatment of black liquor; contacting at least part of the pyrolysed black liquor gas with a catalyst in a second reactor, which is different from the first reactor to provide a conversion treatment to yield a conversion product; and recovering small aromatic compounds from the conversion product.

2. The process according to claim 1, wherein the pyrolysis treatment is carried out without the addition of a catalyst.

3. The process according to claim 1, wherein the wood chips are derived from hardwood.

4. The process according to claim 1, wherein the pyrolysis treatment of black liquor is carried out at a temperature of 350? C. to 700? C. at a pressure of between 0.1 to 6 bara.

5. The process according to claim 1, wherein at least a part of the solid mass is collected and heated to a temperature that is sufficiently high to recover the salt in the solid mass.

6. The process according to claim 1, wherein the conversion treatment involves the conversion of complex aromatic compounds to small aromatic compounds, the conversion of oxygen containing aromatic and oxygen containing aliphatic compounds to small aromatic compounds without oxygen atoms, and/or the conversion of hydrocarbons, such as olefins into small aromatic compounds.

7. The process according to claim 1, wherein the conversion treatment occurs at a temperature between 200? C. and 1000? C.

8. The process according to claim 1, wherein in the conversion treatment the catalyst is present in a weight ratio of pyrolysed black liquor gas to catalyst in the range of 5:1 to 1:20.

9. The process according to claim 1, wherein the catalyst is a zeolitic catalyst, suitably selected from aluminosilicates, SAPOs, silicalites and/or combinations thereof.

10. The process according to claim 1, wherein the catalyst is acidic, and/or is preferably made acidic by ion exchange with ammonium salts and subsequent calcination.

11. The process according to claim 1, wherein the catalyst has a silica alumina ratio from 5 to 300.

12. The process according to claim 1, wherein the catalyst has a largest internal pore size in the range of 4.5 to 12 ?.

13. The process according to claim 1, wherein the catalyst is selected from the group consisting of ZSM-5, ZSM-11, ZSM-35, ZSM-23, ferrierite, zeolite beta, zeolite Y, zeolite X, mordenite, zeolite A, IM-5, SSZ-20, SSZ-55, MCM-22, TNU-9, NU-87, ZSM-57, ZSM-48, EU-1, SSZ-35, SSZ-44, Utrastable Y (US-Y), SBA-15, AL-SBA15, ZSM-18, LZ-135, ZSM-10, MCM-68, SSZ-57, ECR-1, ITQ-25, COK-14, MOR, ZSM-12 SSZ-48 and combinations thereof.

14. The process according to claim 1, wherein the catalyst is bound by means of a binder to form a bound catalyst, and wherein the binder is selected from the group consisting of alumina, silica, silica alumina, titania, zirconia, kaolin and mixtures thereof.

15. The process according to claim 1, wherein the amount of binder in the bound catalyst is in the range of 0 to 80% wt, based on the weight of the bound catalyst.

16. The process according to claim 1, wherein the conversion treatment is carried out in a fixed bed, moving bed or fluidized bed.

17. The process according to claim 1, wherein the recovering of aromatic compounds occurs by subjecting the conversion product to fractionation yielding fraction enriched in small aromatic compounds.

Description

[0043] The invention will be further elucidated by means of the following examples and figures.

[0044] FIG. 1 shows a chromatographic diagram of the chromatography of pyrolysed black liquor gas that has been treated with a catalyst in a gram scale experiment.

[0045] FIG. 2 shows a chromatographic diagram of the chromatography of pyrolysed black liquor gas that has been treated with a catalyst in an auger reactor.

[0046] FIG. 3 shows the Flame ionization detector (FID) analysis obtained in gas chromatographic analysis providing the relative amount of benzene, toluene, xylene (BTX); other mono-aromatics; naphtalenes; azulenes and other aromatic compounds.

[0047] FIG. 4 shows a diagram of the results of a GC-MS analysis of small aromatic compounds in wt % of several biomass sources that have been treated according to the process of the invention. wt % is the weight of small aromatic compounds with respect to the amount of organics in the starting biomass material.

EXAMPLES

[0048] 1. Pyrolysis from Black Liquor and Subsequent Conversion of Pyrolysed Black Liquor Gas Via a Gram Scale Reactor Unit

[0049] Black liquor was obtained from a standard Kraft process using Eucalyptus wood as the predominant feed and was freeze dried (BLFD). The BLFD is first pyrolysed and subsequently up-graded using a gram-scale reactor set up comprising a pyrolysing unit and an up-grading unit, which are connected with each other. A constant stream of N2 of 7 min/ml was used as a gas flow in order to maintain an inert atmosphere. The pyrolysing unit was filled with about 1.5-2.0 g BLFD and the upgrading unit was filled with about 10 gram of H-ZSM-5 catalyst. The gram-scale reactor set up was placed in a fluidized sand bed (T=510? C.) in a way that the upgrading unit is placed first in the fluidizing bed, so that the unit becomes 510? C. and then the pyrolysing unit comprising the BLFD was brought in the fluidizing bed so that the pyrolysis starts at a temperature of 510? C. The pyrolysis takes about 1.5-15 min. The pyrolysis reaction induces an increasing gas flow due to the gasses that are produced. The pyrolysis is finished from the moment that the gas flow has again about the same flow as the initial N2 flow. The obtained pyrolysed black liquor gas is subsequently converted in the upgrading unit via catalytic treatment. The converted pyrolysed black liquor gas was subsequently condensed by bringing the gas to a temperature of ?15? C. in a cooling unit. The cooling unit was then washed with small amounts of petroleum ether (pet-ether). Through a phase separation of the condensate, the water layer was separated from the organic layer. The water layer amounts to 20.1 wt % based on the weight of BLFD. The amount of condensed and converted pyrolysed black liquor which remains in the organic phase amounted to 20.2 wt % based on the weight of BLFD.

[0050] FIG. 1 shows a gas chromatographic analysis of the separated organic layer, which is thus freeze-dried black liquor pyrolysed at 510? C. and that is catalytically converted and than condensed. In order to exclude for large quantities pet-ether present, the chromatogram only shows peaks arising after 4 minutes.

[0051] As shown in FIG. 1, GC-MS analysis shows that the black liquor can be converted to small aromatic compounds such as benzene, toluene and xylene.

2. Aromatics Derived from Pyrolysing Black Liquor which is Subsequent Converted Using an Auger Reactor

[0052] Black liquor was obtained from a standard Kraft process using Eucalyptus wood as the predominant feed. Pyrolysis experiments of black liquor were carried out in a continuously operating mini-plant using Auger reactor technology. Under an inert atmosphere (N2 flow of 125 ml/min) black liquor (218 ml, 390 gram, total solids 71.7%) is fed into the pyrolysis reactor and intensively mixed with sand at a temperature of 500? C. Subsequently the pyrolysed black liquor vapors were contacted under a continuous N2 stream with a pre-heated fixed bed catalyst mixture (280 gram H-ZSM-5(23)) at T=550? C. for further conversion. The obtained conversion product is condensed at T=?15? C., followed by cooling with a subsequent cold trap (liquid nitrogen, T=?196? C.). All condensate units were washed with an organic solvent (pet-ether) in order to collect all condensates. The organic layer was separated from the water layer and concentrated on a rotavap (yield 2.70 g, not optimized).

[0053] FIG. 2 shows a gas chromatographic diagram of pyrolysed black liquor in pet-ether that has been treated with an H-ZSM-5 catalyst according to the above-described procedure performed in an auger reactor. Besides the mono-aromatics benzene (Rf=4.90), toluene (Rf=6.16), p-xylene (7.71), o,m-xylene (8.18) also higher aromatics are being formed under the conditions used.

[0054] FIG. 3 depicts, based upon the FID values obtained in the GC analysis, the ratio between BTX (benzene, toluene, xylenes), other mono-aromatics, naphtalenes, azulens and other aromatic compounds under the reaction conditions formed.

3. Black Liquor Derived from Hardwood Compared with Other Biomass Sources

[0055] Several sources of biomass where treated. Kraft Northern/Southern Hardwood, is black liquor prepared using the Kraft treatment of hardwood chips. Soda Southern Hardwood is black liquor prepared using the soda aq treatment of hardwood wood chips.

Hybrid poplar is wood chips coming from hardwood hybrid poplar.
Pinewood is wood chips coming from a pine tree.
Kraft lignin is lignin derived from black liquor that was prepared by Kraft treatment.

[0056] The biomass sources were all treated in the same way using a Frontier Lab tandem micro reactor model (RX-3050TR) equipped with a single shot sampler (PY1-1040), that is mounted on a gas chromatograph-mass spectrometer (GC-MS). The first reactor pyrolyzes the biomass at 500? C. The pyrolysed biomass gas coming from the first reactor is converted in a second different reactor comprising H-ZSM-5 catalyst at 600? C. The pyrolysis reactor is loaded with 1.0-1.5 mg of black liquor. The catalyst reactor is loaded with approximately 8 mg of catalyst. The catalyst is used for several subsequent experiments without regeneration. The converted pyrolysed black liquor gas was immediately analyzed by the GC-MS.

[0057] Analysis of the products were performed by a gas chromatograph (GC) using a Hewlett Packard 5890 series equipped with a Restek Rx1-5Sil column (length 30 m, diameter 0.25 mm and film 10 ?m) and an mass spectrometer (MS) Hewlett Packard 5972 series detector. The injection temperature was set to 280? C., with a split of 50:1.

[0058] FIG. 4 shows the results of the GC-MS analysis of the several small aromatics that are formed using several biomass materials. Black liquor from hardwood has a higher yield in small aromatic compounds compared with other biomass sources.